Purifying process of tetrakis(fluoroaryl)borate.magnesium halide, tetrakis(fluoroaryl)borate·ether complex and producing process of the same, and producing process of tetrakis(fluoroaryl)borate derivative

ABSTRACT

Tetrakis (fluoroaryl)borate.magnesium halide (Ar 4 BMgX) expressed by General Formula (1):                    
     where each of R 1 -R 10  represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R 1 -R 5  represents a fluorine atom and at least one of R 6 -R 10  represents a fluorine atom, X represents a chlorine atom, a bromine atom, or an iodide atom, and n represents 2 or 3, 
     is treated with alkali metal salts of carboxylic acid and/or alkali earth metal salts of carboxylic acid. Then, a tetrakis(fluoroaryl)borate derivative (Ar 4 BZ) is produced by reacting treated Ar 4 BMgX with a compound generating monovalent cation seeds (for example, N,N-dimethylaniline.hydrochloride). Consequently, it has become possible to provide a purifying process of separating/removing impurities from Ar 4 BMgX readily and efficiently, and a process of producing inexpensive Ar 4 BX efficiently.

This application is a divisional application of U.S. application Ser.No. 09/171,832 filed on Oct. 26, 1998, now U.S. Pat. No. 6,215,025,which is the national phase under 35 U.S.C. §371 of prior PCTInternational Application No. PCT/JP98/00946 which has an Internationalfiling date of Mar. 9, 1998 which designated the United States ofAmerica, the entire contents of which are hereby incorporated byreference.

TECHNICAL FIELD

The present invention relates to {circle around (1)} a purifying processof tetrakis(fluoroaryl)borate.magnesium halide. The present inventionalso relates to {circle around (2)} a tetrakis(fluoroaryl)borate.ethercomplex, which is useful as, for example, a co-catalyst of a metallocenecatalyst (polymeric catalyst) used in a cationic complex polymerizationreaction, a photopolymeric catalyst for silicone, a cationicpolymerization initiator used in the polymerization of a functionalpolymer or monomer with photochemical activation or irradiation ofelectron beams, and an intermediate for producingtetrakis(pentafluorophenyl)borate derivatives of various kinds, and to aprocess of producing the same; and to {circle around (3)} a process ofproducing a tetrakis(fluoroaryl)borate derivative. Further, the presentinvention relates to {circle around (4)} a tetrakis(fluoroaryl)boratederivative.ether complex useful as an intermediate for producing thetetrakis(fluoroaryl)borate derivative and a process of producing thesame, and to {circle around (5)} a process of producingtetrakis(fluoroaryl)borate.

TECHNICAL BACKGROUND

A tetrakis (fluoroaryl) borate derivative is an useful compound as, forexample, a co-catalyst for promoting the activity of a metallocenecatalyst (polymeric catalyst) used in a cationic complex polymerizationreaction, or a photopolymeric catalyst for silicone. Also,tetrakis(fluoroaryl)borate.magnesium halide is an useful compound as anintermediate for producing the tetrakis(fluoroaryl)borate derivative.Recently, the metallocene catalyst has been receiving considerableattention as a polyolefin polymeric catalyst.

A producing process of tetrakis(pentafluorophenyl)borate.magnesiumbromide, which is a kind of tetrakis(fluoroaryl)borate.magnesium halide,from bromopentafluorobenzene through the Grignard reaction is disclosedin, for example, Japanese Laid-open Patent Application No. 247980/1994(Tokukaihei No. 6-247980).

Also, in Japanese Laid-open Patent Application No. 247981/1994(Tokukaihei No. 6-247981), a process of synthesizingtetrakis(pentafluorophenyl)borate.lithium from pentafluorobenzene usingan organic lithium compound and boron halide first, and thence reactingthe resulting compound with N,N-dimethylaniline.hydrochloride isdisclosed as a process of producing a tetrakis(pentafluorophenyl)boratederivative, which is a kind of the tetrakis(fluoroaryl)boratederivative.

Further, a process of producing the tetrakis(pentafluorophenyl)boratederivative by reacting tetrakis(pentafluorophenyl)borate.magnesiumbromide with N,N-dimethylaniline.hydrochloride is disclosed in U.S. Pat.No. 398,236.

However, Japanese Laid-open Patent Application No. 247980/1994(Tokukaihei No. 6-247980) neither discloses nor implies theseparation/removal of magnesium halide, a by-product produced withtetrakis(pentafluorophenyl)borate.magnesium bromide, from the reactionseries. If the tetrakis(pentafluorophenyl)borate derivative is producedfrom tetrakis(pentafluorophenyl)borate.magnesium bromide containingmagnesium halide as impurities, and used as a co-catalyst of themetallocene catalyst, for example, the activity of the metallocenecatalyst deteriorates considerably. The process disclosed in JapaneseLaid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980)is a producing process of tetrakis(pentafluorophenyl)borate.magnesiumbromide containing magnesium halide as impurities. Thus,tetrakis(pentafluorophenyl)borate.magnesium bromide obtained throughthis process can not be used as an adequate intermediate for producingthe tetrakis(pentafluorophenyl)borate derivative.

If typical alkali treatment is applied totetrakis(pentafluorophenyl)borate.magnesium bromide to remove magnesiumhalide from tetrakis(pentaflurorphenyl)borate.magnesium bromide obtainedby the process disclosed in the above publication, magnesium hydroxideis produced. Since magnesium hydroxide turns a post-treatment solutioninto gel, the solution can not be filtered. In other words, sincemagnesium halide can not be removed by the typical alkali treatment, itis difficult to separate tetrakis(pentafluorophenyl)borate.magnesiumbromide obtained in the above process, or to obtain a highly-puretetrakis(fluoroaryl)borate compound after the treatment.

Thus, there has been an increasing demand for a purifying process forseparating/removing impurities, such as magnesium halide, fromtetrakis(fluoroaryl)borate.magnesium halide readily and efficiently.

On the other hand, the process disclosed in Japanese Laid-open PatentApplication No. 247981/1994 (Tokukaihei No. 6-247981) has the followingproblems:

(1) since the reaction series must be kept at −65° C. or below, not onlyspecial equipment is required, but also the cooling cost is high;

(2) the process demands an expensive organic lithium compound (t-butyllithium), which is a dangerous compound because it may ignite whenreacted with water and the like;

(3) the process also demands expensive boron halide (boron trichloride),which is very difficult to handle because it is in the gaseous state andcorrosive. Thus, the process disclosed in the above publication can notbe readily adopted for industrial use.

In the process disclosed in U.S. Pat. No. 5,473,036, magnesium hydroxideis produced as a by-product with the object product, that is, thetetrakis(pentafluorophenyl)borate derivative. Since magnesium hydroxideturns a post-treatment solution into gel, it is difficult to separate(isolate) the tetrakis(pentafluorophenyl)borate derivative from thesolution. Thus, there arises a problem that thetetrakis(pentafluorophenyl)borate derivative can not be producedefficiently.

In other words, the conventional producing processes have a problem thatan inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative cannot be produced efficiently. Hence, there has been an increasing demandfor a process of producing an inexpensive and highly-puretetrakis(fluoroaryl)borate derivative efficiently.

Therefore, it is a first object of the present invention to provide apurifying process of separating/removing impurities, such as magnesiumhalide, from tetrakis(fluoroaryl)borate.magnesium halide readily andefficiently. Also, it is a second object of the present invention toprovide a process of efficiently producing an inexpensive andhighly-pure tetrakis (fluoroaryl)borate derivative, which is useful as,for example, a co-catalyst of the metallocene catalyst or aphotopolymeric catalyst for silicone.

A process of producing tetrakis(pentafluorophenyl)borate, which isuseful as an intermediate for producing thetetrakis(pentafluorophenyl)borate derivatives of various kinds, has beenknown.

For example, a process of obtainingtetrakis(pentafluorophenyl)borate.lithium by reacting pentafluorophenyllithium, which is produced by reacting pentafluorophenyl bromide withbutyl lithium at −78° C. in dry pentane, withtris(pentafluorophenyl)borate at −78° C. in dry pentane is disclosed inp245, J. Organometallic. Chem., 2, (1964).

Also, aforementioned Japanese Laid-open Patent Application No.247981/1994 (Tokukaihei No. 6-247981) discloses a process of preparingtetrakis(pentafluorophenyl)borate.lithium used in the producing processof N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate fromN,N-dimethylaniline.hydrochloride as follows.

That is, the above publication discloses a process of preparing, inwhich pentafluorophenyl lithium is produced initially by reactingpentafluorophenyl bromide with t-butyl lithium at −65° C. in dry diethylether, and then tetrakis(pentafluorophenyl)borate.lithium is prepared byreacting the resulting pentafluorophenyl lithium with boron trichlorideat −65° C. to −55° C. in dry pentane.

However, the process disclosed in p245, J. Organometallic. Chem., 2,(1964) has a problem that the yield oftetrakis(pentafluorophenyl)borate.lithium is low (43%). Also, since theprocess disclosed in aforementioned Japanese Laid-open PatentApplication No. 247981/1994 (Tokukaihei No. 6-247981) has theabove-explained problem, it can not be readily applied to industrialuse.

On the other hand, aforementioned Japanese Laid-open Patent ApplicationNo. 247980/1994 (Tokukaihei No. 6-247980) discloses a process ofobtaining the tetrakis(pentafluorophenyl)borate derivative by reactingpentafluorophenyl magnesium bromide, which is a Grignard reagent, with aboron trifluoride-diethyl ether complex.

Also, aforementioned U.S. Pat. No. 5,473,036 discloses a process ofobtaining tetrakis(pentafluorophenyl)borate.magnesium bromide byreacting pentafluorophenyl magnesium bromide, which is a Grignardreagent, with a boron trifluoride.diethyl ether complex, and a processof obtaining N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate byreacting tetrakis(pentafluorophenyl)borate.magnesium bromide with anaqueous solution of N,N-dimethylaniline.hydrochloride.

However, in the process disclosed in Japanese Laid-open PatentApplication No. 247980/1994 (Tokukaihei No. 6-247980), magnesium halide,such as magnesium bromide fluoride (MgBrF), produced as a by-productwith tetrakis(pentafluorophenyl)borate.magnesium bromide, is notseparated/removed from the reaction series and remains therein asimpurities. Thus, as previously mentioned, if thetetrakis(pentafluorophenyl)borate derivative is produced fromtetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesiumhalide as impurities and used as a co-catalyst of the metallocenecatalyst, for example, the activity of the metallocene catalystdeteriorates considerably.

Further, in the processes disclosed in U.S. Pat. No. 398,236 andJapanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No.6-247980), resulting tetrakis(pentafluorophenyl)borate.magnesium bromideis colored with a coloring component derived from the Grignard reaction.Thus, if the tetrakis(pentafluorophenyl)borate derivative is producedfrom tetrakis(pentafluorophenyl)borate.magnesium bromide obtained ineither of the above processes, there arises a problem that the coloringcomponent remains in the tetrakis(pentafluorophenyl)borate derivative(the tetrakis(pentafluorophenyl)borate derivative is colored).

The process of producing tetrakis(pentafluorophenyl)borate derivativedisclosed in U.S. Pat. No. 398,236 also has the following problem. Thatis, in the above process, a post-treatment solution is turned into gelby magnesium hydroxide produced as a by-product. Thus, it is difficultto filter the solution and isolate the tetrakis(pentafluorophenyl)boratederivative from the solution. Also, to isolate thetetrakis(pentafluorophenyl)borate derivative in the above process, acrude product must be crystallized again using a chlorine solvent, suchas chloroform and dichloroethane.

As has been explained, since tetrakis(fluoroaryl)borate.magnesiumbromide obtained by the conventional processes contains the by-productsalts and coloring component as impurities, it can not be used as anadequate intermediate for producing the tetrakis (fluoroaryl)boratederivative. Hence, there has been an increasing demand for atetrakis(fluoroaryl)borate derivative which can be used as a suitableintermediate for producing the tetrakis(fluoroaryl)borate derivatives ofvarious kinds.

It is therefore a third object of the present invention to provide atetrakis(fluoroaryl)borate.ether complex as a new material which can beused suitably as a co-catalyst of the metallocene catalyst, a cationicpolymerization initiator, an intermediate for producing thetetrakis(fluoroaryl)borate derivatives of various kinds and the like,and a producing process of the same.

Also, the conventional producing processes of thetetrakis(fluoroaryl)borate derivative from tetrakis(fluoroaryl)borateprepared using an organic lithium compound or a Grignard reagent has aproblem that an inexpensive and highly-pure tetrakis(fluoroaryl)boratederivative can not be produced efficiently.

It is therefore a fourth object of the present invention to provide aprocess of producing an inexpensive and highly-puretetrakis(fluoroaryl)borate derivative efficiently. Also, it is a fifthobject of the present invention to provide a process of producinghighly-pure tetrakis(fluoroaryl)borate. Further, it is a sixth object ofthe present invention to provide a tetrakis(fluoroaryl)boratederivative.ether complex as a new material, which is useful not only asan intermediate for producing the tetrakis(fluoroaryl)borate derivative,but also as a co-catalyst of the metallocene catalyst (polymericcatalyst) used in the cationic complex polymerization reaction, and aprocess of producing the same. Furthermore, it is a seventh object ofthe present invention to provide a process of producing an inexpensivetetrakis(fluoroaryl)borate derivative from thetetrakis(fluoroaryl)borate derivative.ether complex efficiently.

To fulfill the first and second objects, the inventors of the presentinvention conducted an assiduous study on the process of purifyingtetrakis(fluoroaryl)borate.magnesium halide and the process of producingthe tetrakis(fluoroaryl)borate derivative. In due course, the inventorsachieved the present invention when they discovered that:

the impurities, such as magnesium halide, can be readily and efficientlyseparated/removed from tetrakis(fluoroaryl)borate.magnesium halide bytreating tetrakis(fluoroaryl)borate.magnesium halide with, for example,alkali metal salts of carboxylic acid and/or alkaline earth metal saltsof carboxylic acid; and

an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative,which is useful as, for example, a co-catalyst of the metallocenecatalyst or a photopolymeric catalyst for silicone, can be producedefficiently by reacting a tetrakis(fluoroaryl)borate compound obtainedthrough the above purifying process with a compound generatingmonovalent cationic compounds.

In other words, to fulfill the above objects, a process of purifyingtetrakis(fluoroaryl)borate.magnesium halide of the present invention ischaracterized by treating tetrakis(fluoroaryl)borate.magnesium halideexpressed by General Formula (1):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, X represents a chlorine atom, a bromine atom, or aniodide atom, and n represents 2 or 3, with:

{circle around (1)} alkali metal salts of carboxylic acid and/oralkaline earth metal salts of carboxylic acid;

{circle around (2)} an acid;

{circle around (3)} an acid followed by alkali metal hydroxide and/oralkaline earth metal hydroxide; or

{circle around (4)} an acid followed by alkali metal salts of carboxylicacid and/or alkaline earth metal salts of carboxylic acid.

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, X represents a chlorine atom, a bromine atom, or aniodide atom, and n represents 2 or 3, with:

{circle around (1)} alkali metal salts of carboxylic acid and/or alkaliearth metal salts of carboxylic acid;

{circle around (2)} an acid;

{circle around (3)} an acid followed by alkali metal hydroxide and/oralkali earth metal hydroxide; or

{circle around (4)} an acid followed by alkali metal salts of carboxylicacid and/or alkali earth metal salts of carboxylic acid.

According to the above process, magnesium halide, such as magnesiumbromide fluoride, produced as a by-product during the producing processof tetrakis(fluoroaryl)borate.magnesium halide through the Grignardreaction can be turned into water-soluble or water-insoluble magnesiumsalts (that is, in the state of salts other than magnesium hydroxide).Thus, the salts can be readily and efficiently separated/removed fromtetrakis(fluoroaryl)borate.magnesium halide through oil-waterseparation, filtration or the like. In short, the impurities, such asmagnesium halide, can be readily and efficiently separated/removed fromtetrakis(fluoroaryl)borate.magnesium halide.

When tetrakis(fluoroaryl)borate.magnesium halide is treated with thepurifying process {circle around (1)}, {circle around (3)} or {circlearound (4)}, alkali metal salts and/or alkaline earth metal salts oftetrakis(fluoroaryl)borate can be obtained. Whentetrakis(fluoroaryl)borate.magnesium halide is treated with thepurifying process {circle around (2)}, hydrogen compound oftetrakis(fluoroaryl)borate can be obtained.

A process of producing a tetrakis(fluoroaryl)borate derivative of thepresent invention relates to a process of producing atetrakis(fluoroaryl)borate derivative expressed by General Formula (2):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, Z+ represents a monovalent cation seed, and n represents2 or 3, and is characterized by reacting a tetrakis(fluoroaryl)boratecompound obtained by any of the purifying processes {circle around(1)}-{circle around (4)} with a compound generating monovalent cationcompounds.

According to the above process, an inexpensivetetrakis(fluoroaryl)borate derivative can be produced efficiently fromthe tetrakis(fluoroaryl)borate compound obtained through any of theabove purifying processes, namely, alkali metal salts, alkaline earthmetal salts, and hydrogen compounds of tetrakis(fluoroaryl)borate. Theresulting tetrakis(fluoroaryl)borate derivative does not contain theimpurities, such as magnesium halide, and therefore is so pure that itcan be used suitably as, for example, a co-catalyst of the metallocenecatalyst used in the cationic complex polymerization reaction orphotopolymeric catalyst for silicone.

Also, to fulfill the third object, the inventors of the presentinvention conducted an assiduous study on thetetrakis(fluoroaryl)borate.ether complex and the process of producingthe same. In due course, the inventors discovered that an inexpensiveand highly-pure tetrakis(fluoroaryl)borate.ether complex as a newmaterial, which can be suitably used as an intermediate for producingthe tetrakis(fluoroaryl)borate derivatives of various kinds, can beobtained at high yield by reacting tetrakis(fluoroaryl)borate with aparticular kind of ether compound.

In addition, the inventors achieved the present invention when they alsodiscovered that even when tetrakis(fluoroaryl)borate.magnesium halidecontaining a coloring component derived from the Grignard reaction andby-product salts, such as magnesium bromide fluoride (MgBrF) produced asa by-product in the Grignard reaction, is used as a raw material, thatis, tetrakis(fluoroaryl)borate, a tetrakis(fluoroaryl)borate.ethercomplex can be obtained in the form of highly-pure crystals, from whichthe coloring component and by-product salts can be readilyseparated/removed.

In other words, a process of producing atetrakis(fluoroaryl)borate.ether complex of the present inventionrelates to a process of producing a tetrakis(fluoroaryl)borate.ethercomplex expressed by Formula (4):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, each of R₁₁ and R₁₂ represents a hydrocarbon group whichmay include a substituent group containing a hetero atom, Y represents abivalent hydrocarbon group, M represents a hydrogen atom, alkali metal,alkaline earth metal, or alkaline earth metal halide, n represents 2 or3, and m represents 1 when M represents a hydrogen atom, alkali metal,or alkaline earth metal halide, and 2 when M represents alkaline earthmetal, and is characterized by reacting tetrakis(fluoroaryl)borateexpressed by Formula (5):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, M represents a hydrogen atom, alkali metal, alkalineearth metal, or alkaline earth metal halide, n represents 2 or 3, and mrepresents 1 when M represents a hydrogen atom, alkali metal, oralkaline earth metal halide, and 2 when M represents alkaline earthmetal,

with an ether compound expressed by General Formula (6):

R₁₁—O—Y—O—R₁₂  (6)

 where each of R₁₁ and R₁₂ represents a hydrocarbon group which mayinclude a substituent group containing a hetero atom, and Y represents ahydrocarbon bivalent group.

According to the above process, an inexpensive and highly-puretetrakis(fluoroaryl)borate.ether complex as a new material suitably usedas, for example, a co-catalyst of the metallocene catalyst, a cationicpolymerization initiator, or an intermediate for producing thetetrakis(fluoroaryl)borate derivatives of various kinds, can be producedat high yield.

Further, to fulfill the fourth through seventh objects, the inventors ofthe present invention conducted an assiduous study. In due course, theinventors achieved the present invention when they discovered that aninexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can beproduced efficiently when both a particular kind oftetrakis(fluoroaryl)borate.ether complex and a compound generatingmonovalent cationic compounds are used as a starting material.

Further, to fulfill the fourth through seventh objects, the inventors ofthe present invention conducted an assiduous study. In due course, theinventors achieved the present invention when they discovered that aninexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can beproduced efficiently when both a particular kind oftetrakis(fluoroaryl)borate.ether complex and a compound generatingmonovalent cation seeds are used as a starting material.

In other words, to fulfill the above objects, a process of producing thetetrakis(fluoroaryl)borate derivative of the present invention expressedby Formula (2) above is characterized by using both thetetrakis(fluoroaryl)borate.ether complex expressed by Formula (4) aboveand a compound generating monovalent cationic compounds as a startingmaterial.

According to the above process, since thetetrakis(fluoroaryl)borate.ether complex expressed by General Formula(4) above, which can be readily and highly purified compared withtetrakis(fluoroaryl)borate, is used as the starting material, thetetrakis(fluoroaryl)borate derivative expressed by General Formula (2)above can be produced efficiently with high purity at low costs.

In addition, to fulfill the above objects, a process of producingtetrakis(fluoroaryl)borate expressed by Formula (5) above ischaracterized by removing the ether compound expressed by Formula (6)above from the tetrakis(fluoroaryl)borate.ether complex expressed byFormula (4) above.

According to the above processes, since thetetrakis(fluoroaryl)borate.ether complex expressed by General Formula(4) above, which can be readily and highly purified compared withtetrakis (fluoroaryl)borate, is used, highly-puretetrakis(fluoroaryl)borate can be produced compared with theconventional process of producing tetrakis(fluoroaryl)borate directlyfrom an organic lithium compound or a Grignard reagent.

Further, a process of producin g a tetrakis(fluoroaryl)boratederivative.ether complex of the present invention relates to a processof producing a tetrakis(fluoroaryl)borate derivative.ether complexexpressed by General Formula (7):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, each of R₁₁ and R₁₂ represents a hydrocarbon group whichmay include a substituent group containing a hetero atom, Y represents abivalent hydrocarbon group, Z+ represents a monovalent cationiccompound, and n represents 2 or 3, and is characterized by reacting thetetrakis(fluoroaryl)borate.ether complex expressed by Formula (4) abovewith a compound generating monovalent cationic compounds.

According to the above process, the tetrakis(fluoroaryl)boratederivative.ether complex expressed as General Formula (7) above as anew, useful material for an intermediate in producing thetetrakis(fluoroaryl)borate derivative can be produced.

Further, to fulfill the above objects, a process of producing thetetrakis(fluoroaryl)borate derivative of the present invention expressedby Formula (2) above is characterized by removing the ether compoundexpressed by Formula (6) above from the tetrakis(fluoroaryl)boratederivative.ether complex expressed by Formula (7) above.

According to the above process, the tetrakis(fluoroaryl)boratederivative expressed by General Formula (2) above can be produced fromthe tetrakis(fluoroaryl)borate derivative.ether complex expressed byGeneral Formula (7) above efficiently at low costs. DISCLOSURE OF THEINVENTION

The purifying process of the tetrakis(fluoroaryl)borate.magnesium halideof the present invention expressed by General Formula (1) above is aprocess of applying the treatment with:

{circle around (1)} alkali metal salts of carboxylic acid and/oralkaline earth metal salts of carboxylic acid;

{circle around (2)} an acid;

{circle around (3)} an acid followed by alkali metal hydroxide and/oralkaline earth metal hydroxide; or

{circle around (4)} an acid followed by alkali metal salts of carboxylicacid and/or alkaline earth metal salts of carboxylic acid.

Also, the process of producing the tetrakis(fluoroaryl)borate derivativeof the present invention expressed by Formula (2) above is a process ofreacting a tetrakis(fluoroaryl)borate compound obtained by any of thepurifying processes {circle around (1)}-{circle around (4)} with acompound generating monovalent cationic compounds.

Here, the tetrakis(fluoroaryl)borate compound means alkali salts,alkaline earth metal salts, and hydrogen compounds oftetrakis(fluoroaryl)borate. The tetrakis(fluoroaryl)borate.magnesiumhalide and tetrakis(fluoroaryl)borate compound are suitable as anintermediate of the tetrakis(fluoroaryl)borate derivative.

Tetrakis(fluoroaryl)borate.magnesium halide treated in the presentinvention is a compound, in which each of substituents denoted as R₁-R₁₀is a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxygroup, provided that at least one of R₁-R₅ is a fluorine atom and atleast one of R₆-R₁₀ is a fluorine atom, a substituent denoted as X is achlorine atom, a bromine atom, or an iodide atom, and n represents 2 or3.

Examples of the hydrocarbon group include: aryl group, a straight-chain,branched-chain, or cyclic alkyl group having up to 12 carbon atoms, astraight-chain, branched-chain, or cyclic alkenyl group having 2-12carbon atoms, etc. The hydrocarbon group may further include afunctional group that remains inactive to the treatment carried out andreactions taking place in the present invention. Examples of thefunctional group include: a methoxy group, a methylthio group, anN,N-dimethylamino group, an o-anise group, a p-anise group, atrimethylsilyl group, a dimethyl-t-butyl silyloxy group, atrifluoromethyl group, etc.

The alkoxy group is expressed by General Formula (A):

—OR_(a)  (A)

where R_(a) represents a hydrocarbon group. Examples of the hydrocarbongroup denoted as R_(a) in the formula are: an aryl group, astraight-chain, branched-chain, or cyclic alkyl group having up to 12carbon atoms, a straight-chain, branched-chain, or cyclic alkenyl grouphaving 2-12 carbon atoms. The hydrocarbon group may further include afunctional group that remains inactive to the treatment carried out andreactions taking place in the present invention.

Examples of the alkoxy group expressed by General Formula (A) above are:a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxygroup, an n-butoxy group, an isobutoxy group, a sec-butoxy group, at-butoxy group, a cyclohexyloxy group, an allyloxy group, a phenoxygroup, etc.

Of all kinds of tetrakis(fluoroaryl)borate magnesium halide expressed byGeneral Formula (1) above, the most preferred istetrakis(pentafluorophenyl)borate.magnesium bromide.

A process of producing tetrakis(fluoroaryl)borate.magnesium halide isnot especially limited. Tetrakis(fluoroaryl)borate.magnesium halide canbe readily obtained by, for example: i) a process of reacting fluoroarylmagnesium halide as a Grignard reagent with boron halide in the moleratio of 4:1; ii) a process of reacting fluoroaryl magnesium halide withtris(fluoroaryl)borane in the mole ratio of 1:1; etc. The reactionconditions of the Grignard reaction in these processes are notespecially limited.

Tetrakis(fluoroaryl)borate.magnesium halide is obtained in the form of asolution dissolved into a solvent used in the Grignard reaction.Examples of the solvent include, but not limited to:

ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether,and anisole;

aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane;

alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane;

aromatic hydrocarbon solvents, such as benzene and toluene; etc.

A mixture of these solvents can be used as well. In case thattetrakis(fluoroaryl)borate.magnesium halide is produced by reactingfluoroaryl magnesium halide with boron halide, magnesium halide, such asmagnesium bromide fluoride, produced as a by-product is dissolved intothe solution as the impurities.

Examples of the alkali metal salts of carboxylic acid used in thepurifying process {circle around (1)} or {circle around (4)} of thepresent invention include, but not limited to:

alkali metal salts of saturated aliphatic monocarboxylic acid, such assodium formate, potassium formate, sodium acetate, potassium acetate,sodium propionate, and potassium propionate;

mono- or dialkali metal salts of saturated aliphatic dicarboxylic acid,such as sodium oxalate monobasic, sodium oxalate dibasic, potassiumoxalate monobasic, potassium oxalate dibasic, sodium malonate monobasic,sodium malonate dibasic, potassium malonate monobasic, potassiummalonate dibasic, sodium succinate monobasic, sodium succinate dibasic,potassium succinate monobasic, and potassium succinate dibasic;

alkali metal salts of unsaturated aliphatic monocarboxylic acid, such assodium acrylate, potassium acrylate, sodium methacrylate, and potassiummethacrylate;

mono- or dialkali metal salts of unsaturated aliphatic dicarboxylicacid, such as sodium maleate monobasic, sodium maleate dibasic,potassium maleate monobasic, potassium maleate dibasic, sodium fumaratemonobasic, sodium fumarate dibasic, potassium fumarate monobasic, andpotassium fumarate dibasic;

alkali metal salts of aromatic monocarboxylic acid, such as sodiumbenzoate and potassium benzoate;

mono- or dialkali metal salts of aromatic dicarboxylic acid, such assodium phthalate monobasic, sodium phthalate dibasic, potassiumphthalate monobasic, potassium phthalate dibasic, sodium isophthalatemonobasic, sodium isophthalate dibasic, potassium isophthalatemonobasic, potassium isophthalate dibasic, sodium terephthalatemonobasic, sodium terephthalate dibasic, potassium terephthalatemonobasic, and potassium terephthalate dibasic; etc. Note that, in thepresent invention, alkali metal salts of carboxylic acid includecarbonates, such as lithium carbonate, sodium carbonate, sodiumhydrocarbonate, potassium carbonate, and potassium hydrocarbonate.

Examples of the alkali earth metal salts of carboxylic acid used in thepurifying process {circle around (1)} or {circle around (4)} of thepresent invention include, but not limited to:

alkali earth metal salts of saturated aliphatic monocarboxylic acid,such as calcium formate, barium formate, calcium acetate, bariumacetate, calcium propionate, and barium propionate;

alkali earth metal salts of saturated aliphatic dicarboxylic acid, suchas calcium oxalate, barium oxalate, calcium malonate, barium malonate,calcium succinate, and barium succinate;

alkali earth metal salts of unsaturated aliphatic monocarboxylic acid,such as calcium acrylate, barium acrylate, calcium methacrylate, andbarium methacrylate;

alkali earth metal salts of unsaturated aliphatic dicarboxylic acid,such as calcium maleate, barium maleate, calcium fumarate, and bariumfumarate;

alkali earth metal salts of aromatic monocarboxylic acid, such ascalcium benzoate and barium benzoate;

alkali earth metal salts of aromatic dicarboxylic acid, such as calciumphthalate, barium phthalate, calcium isophthalate, barium, isophthalate,calcium terephthalate, and barium terephthalate; etc.

In the present invention, the alkali earth metal salts of carboxylicacid include carbonates, such as calcium carbonate and barium carbonate.Note that, however, in the present invention, the alkali earth metalsalts of carboxylic acid do not include magnesium salts of carboxylicacid.

One member or a mixture of two or more members selected from theseexamples of alkali metal salts of carboxylic acid and alkali earth metalsalts of carboxylic acid (hereinafter, collectively referred to ascarboxylate) can be used effectively. Of all the example carboxylates,lithium carbonate, sodium carbonate, potassium carbonate, sodiumacetate, sodium succinate dibasic, and barium acetate are morepreferable than the others. An amount of used carboxylate is notespecially limited, but at least one equivalent of the carboxylate totetrakis(fluoroaryl)borate.magnesium halide must be used. When a mixtureof the alkali metal salts of carboxylic acid and alkali earth metalsalts of carboxylic acid is used, a mixing ratio of these metal salts isnot especially limited.

Examples of the acid used in the purifying process {circle around (2)},{circle around (3)}, or {circle around (4)} include, but not limited to:

inorganic acids, such as hydrochloric acid, sulfuric acid, nitric acid,phosphoric acid, and carbonic acid;

organic acids, such as formic acid, acetic acid, propionic acid, oxalicacid, malonic acid, and succinic acid; etc.

One member or a mixture of two or more members selected from theseexample acids can be used effectively. Of all these example acids,hydrochloric acid, sulfuric acid, formic acid, acetic acid, succinicacid, and malonic acid are more preferable than the others. An amount ofused acid is not especially limited, but at least one equivalent of theacid to magnesium used (charged to the reaction series) when producingtetrakis(fluoroaryl)borate.magnesium halide must be used. In case that amixture of the inorganic acid and organic acid is used, a mixing ratioof these acids is not especially limited.

Examples of alkali metal hydroxide used in the purifying process {circlearound (3)} of the present invention include lithium hydroxide, sodiumhydroxide, potassium hydroxide, etc. Examples of alkali earth metalhydroxide used in the purifying process {circle around (3)} of thepresent invention include calcium hydroxide, barium hydroxide, etc. Notethat, however, in the present invention, alkali earth metal hydroxidedoes not include magnesium hydroxide.

One member or a mixture of two or more members selected from theseexample alkali metal hydroxides and alkali earth metal hydroxides(hereinafter, collectively referred to as hydroxide) can be usedeffectively. An amount of used hydroxide is not especially limited, butat least one equivalent of the hydroxide totetrakis(fluoroaryl)borate.magnesium halide must be used. In case that amixture of alkali metal hydroxide and alkali earth metal hydroxide isused, a mixing ratio of these hydroxides is not especially limited.

In case that tetrakis(fluoroaryl)borate.magnesium halide is treated withthe carboxylate (purifying process {circle around (1)}),tetrakis(fluoroaryl)borate.magnesium halide is mixed with thecarboxylate with stirring. In case thattetrakis(fluoroaryl)borate.magnesium halide is treated with the acid(purifying process {circle around (2)}),tetrakis(fluoroaryl)borate.magnesium halide is mixed with the acid withstirring. In case that tetrakis(fluoroaryl)borate.magnesium halide istreated with the acid followed by the hydroxide (purifying process{circle around (3)}), after the acid is separated/removed,tetrakis(fluoroaryl)borate.magnesium halide is mixed with the hydroxidewith stirring. In case that tetrakis(fluoroaryl)borate.magnesium halideis treated with the acid followed by the carboxylate (purifying process{circle around (4)}), after the acid is separated/removed,tetrakis(fluoroaryl)borate.magnesium halide is mixed with thecarboxylate with stirring.

A method of mixing a solution of tetrakis(fluoroaryl)borate.magnesiumhalide with the carboxylate, acid, or hydroxide is not especiallylimited. The carboxylate, acid, or hydroxide may be mixed with asolution of tetrakis(fluoroaryl)borate.magnesium halide directly (in theform of a solid or a liquid), or optionally, in the form of a solution.

Examples of preferable solvents when using a solution of thecarboxylate, acid, or hydroxide include, but not limited to:

water;

ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether,and anisole;

aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane;

alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane;

ester solvents, such as methyl acetate and ethyl acetate;

aromatic hydrocarbon solvents, such as benzene and toluene;

alcohol solvents, such as methyl alcohol and ethyl alcohol;

ketone solvents, such as acetone and methyl ethyl ketone; etc.

One member or a mixture: of two or more members selected from theseexample solvents can be used effectively.

A method of mixing tetrakis(fluoroaryl)borate.magnesium halide with thecarboxylate, acid, or hydroxide, and a mixing order are not especiallylimited. For example, the carboxylate, acid, or hydroxide may be mixed asolution of tetrakis(fluoroaryl)borate.magnesium halide, or the solutionof tetrakis(fluoroaryl)borate.magnesium halide may be mixed with thecarboxylate, acid, or hydroxide.

A temperature and a time when mixing the solution oftetrakis(fluoroaryl)borate.magnesium halide with the carboxylate, acid,or hydroxide with stirring, that is, the treatment conditions, are notespecially limited. According to the purifying processes {circle around(1)}-{circle around (4)} of the present invention, the solution oftetrakis(fluoroaryl)borate.magnesium halide is mixed with thecarboxylate, acid, or hydroxide, after which the reaction solution isstirred for a certain time at room temperature, wherebytetrakis(fluoroaryl)borate.magnesium halide is readily treated. A methodof separating/removing the acid when treatingtetrakis(fluoroaryl)borate.magnesium halide with the acid followed bythe hydroxide or carboxylate is not especially limited. For example, theacid can be readily separated from a solution of thetetrakis(fluoroaryl)borate compound by a simple manipulation, such asliquid separation (oil-water separation). After the treatment, thetetrakis(fluoroaryl)borate compound is obtained in the form of asolution dissolved into the solvent.

In case that the solution of the tetrakis(fluoroaryl)borate compoundcontains the carboxylate, acid, or hydroxide, the carboxylate, acid, orhydroxide can be removed optionally by washing or the like. In case thatthe carboxylate, acid, or hydroxide, or the solution thereof containsthe tetrakis(fluoroaryl)borate compound, the tetrakis(fluoroaryl)boratecompound can be collected optionally by extraction or the like. Further,in case that the solution of the tetrakis (fluoroaryl)borate compoundcontains water, water can be removed (dried out) optionally by adding adrying agent, such as magnesium sulfate anhydride.

A tetrakis(fluoroaryl)borate compound expressed by General Formula (3):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, Ma represents a hydrogen atom, alkali metal, or alkalineearth metal, n represents 2 or 3, and m represents 1 when Ma representsa hydrogen atom or alkali metal, or 2 when Ma represents alkaline earthmetal, can be obtained by treating tetrakis(fluoroaryl)borate.magnesiumhalide through any of the purifying processes {circle around(1)}-{circle around (4)}.

In other words, when tetrakis(fluoroaryl)borate.magnesium halide istreated with the carboxylate or hydroxide, that is, through thepurifying process {circle around (1)}, {circle around (3)} or {circlearound (4)}, tetrakis(fluoroaryl)borate expressed by Formula (3) above,in which Ma represents alkali metal or alkaline earth metal, can beobtained. Examples of alkali metal are lithium, sodium, potassium, etc.Examples of alkaline earth metal are calcium, barium, etc.

On the other hand, when tetrakis(fluoroaryl)borate.magnesium halide istreated with the acid, that is, through the purifying process {circlearound (2)}, tetrakis(fluoroaryl)borate expressed by General Formula (3)above, in which Ma represents a, hydrogen atom, can be obtained.

Of all the purifying processes {circle around (1)}-{circle around (4)}of the present invention, the optimum purifying process can be selecteddepending on the kinds of tetrakis(fluoroaryl)borate.magnesium halide,solvents and the like, so that the resulting tetrakis(fluoroaryl)boratecompound is in the desired form (alkali metal salts, alkaline earthmetal salts, or hydride), or the post-treatment separatory manipulation,such as liquid separation, can be carried out more readily.

According to any purifying process of the present invention, forexample, magnesium halide, which is produced as a by-product whiletetrakis(fluoroaryl)borate.magnesium halide is produced through theGrignard reaction, can be converted to either water-soluble orwater-insoluble magnesium salts (that is, salts other magnesiumhydroxide). Thus, the salts contained intetrakis(fluoroaryl)borate.magnesium halide can be separated/removedfrom the solution of the tetrakis(fluoroaryl)borate compound readily andefficiently through the manipulation, such as liquid separation andfiltration. In short, the impurities, such as magnesium halide, can beseparated/removed from tetrakis(fluoroaryl)borate.magnesium halidereadily and efficiently. Here, a method of removing/separating theimpurities from the solution of the tetrakis(fluoroaryl)borate compoundis not especially limited.

When tetrakis(fluoroaryl)borate.magnesium halide does not contain theimpurities, such as magnesium halide, it is preferable to obtain thehydrogen compound, alkali metal salts, or alkaline earth metal salts oftetrakis(fluoroaryl)borate through the above treatment. Because, byapplying the above treatment, the reaction with a compound generatingmonovalent cationic compounds can proceed faster and at higher yield.

As has been explained, the purifying processes oftetrakis(fluoroaryl)borate.magnesium halide of the present inventionare:

{circle around (1)} a process of treatingtetrakis(fluoroaryl)borate.magnesium halide with carboxylate;

{circle around (2)} a process of treatingtetrakis(fluoroaryl)borate.magnesium halide with an acid;

{circle around (3)} a process of treatingtetrakis(fluoroaryl)borate.magnesium halide with an acid followed by thehydroxide; and

{circle around (4)} a process of treatingtetrakis(fluoroaryl)borate.magnesium halide with an acid followed by thecarboxylate.

Consequently, it has become possible to provide a purifying process ofseparating/removing the impurities, such as magnesium halide, fromtetrakis(fluoroaryl)borate.magnesium halide readily and efficiently.Also, for example, the reaction of the tetrakis(fluoroaryl)boratecompound obtained by the above purifying process with a compoundgenerating monovalent cationic compounds can proceed faster at higheryield. The tetrakis(fluoroaryl)borate compound can be isolated/purifiedin the form of crystals by removing (distilling out) the solventoptionally.

The compound generating monovalent cationic compounds referred herein(hereinafter, referred to as cationic compound generating compound) canbe any compound which generates monovalent cationic compounds in areaction solvent described below and is reactive with either thetetrakis (fluoroaryl)borate compound or thetetrakis(fluoroaryl)borate.ether complex or tetrakis(fluoroaryl)borate(the compound will be described below).

Examples of the monovalent cationic compounds generated by the cationiccompound seed generating compound include, but not limited to:

ammonium cations, such as n-butyl ammonium, dimethyl ammonium, trimethylammonium, triethyl ammonium, triisopropyl ammonium, tri-n-butylammonium, tetramethyl ammonium, tetraethyl ammonium, and tetra-n-butylammonium;

anilinium cations, such as anilinium, N-methyl anilinium, N,N-dimethylanilinium, N,N-diethyl anilinium, N,N-diphenyl anilinium, andN,N,N-trimethyl anilinium;

pyridinium cations, such as pyridinium, N-methyl pyridinium, andN-benzyl pyridinium;

quinolinium cations, such as quinolinium and isoquinolinium;

phosphonium cations, such as dimethylphenyl phosphonium, triphenylphosphonium, tetraethyl phosphonium, and tetraphenyl phosphonium;

sulfonium cations, such as trimethyl sulfonium and triphenyl sulfonium;

iodonium cations, such as diphenyl iodonium and di-4-methoxy phenyliodonium;

carbenium cations, such as triphenyl carbenium and tri-4-methoxyphenylcarbenium;

monovalent cations of metals other than alkali metal and alkaline earthmetal; etc.

Of all these examples, trialkyl ammonium cation, tetraalkyl ammoniumcation, dialkyl anilinium cation, alkylpyridinium cation, tetraalkylphosphonium cation, tetraaryl phosphonium cation, and diaryl iodoniumcation are more preferable than the others. Here, anion seeds that forma pair with the monovalent cationic compounds are not especiallylimited.

Examples of the cation seed generating compound include:

quaternary ammonium compounds, such as tri-n-butylamine.hydrochloride,N,N-dimethylaniline.hydrochloride, N,N-dimethylaniline.sulfate, andtetramethyl ammonium chloride;

nitrogen-containing aromatic heterocyclic compounds, such aspyridine.hydrochloride, quinoline.hydrochloride, N-methyl pyridineiodide, and N-methyl quinoline iodide;

quaternary phosphonium compounds, such as n-butylphosphonium bromide andtetraphenyl phosphonium bromide;

sulfonium compounds, such as trimethyl sulfonium iodide;

iodinium compounds, such as diphenyl iodinium chloride;

carbenium compounds, such as trityl chloride; etc.

For example, N,N-dimethylaniline.hydrochloride generates N,N-dimethylanilinium cations as the monovalent cation seeds. In this case, theanion seeds are chlorine ions.

An amount of used cationic compound generating compound is notespecially limited, but at least 0.8 equivalent of cationic compoundgenerating compound to the tetrakis(fluoroaryl)borate compound, atetrakis (fluoroaryl)borate.ether complex described below, ortetrakis(fluoroaryl)borate must be used.

The producing process of the tetrakis(fluoroaryl)borate derivative ofthe present invention uses a reaction solvent. Examples of the reactionsolvent include, but not limited to:

water;

ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether,and anisole;

aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane;

alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane;

ester solvents, such as methyl acetate and ethyl acetate;

aromatic hydrocarbon solvents, such as benzene and toluene;

alcohol solvents, such as methyl alcohol and ethyl alcohol;

ketone solvents, such as acetone and methyl ethyl ketone; etc.

One member or a mixture of two or more members selected from theseexample reaction solvents can be used effectively.

In case that the solution of the tetrakis(fluoroaryl)borate compoundobtained by the above treatment is used for the reaction, a solvent, inwhich the tetrakis(fluoroaryl)borate compound is dissolved, can be usedas the reaction solvent (either entirely or partially). Thus, in theproducing process of the tetrakis(fluoroaryl)borate derivative of thepresent invention, after tetrakis(fluoroaryl)borate.magnesium halide istreated, the tetrakis(fluoroaryl)borate derivative can be produced fromthe resulting solution of the tetrakis(fluoroaryl)borate compoundwithout isolating the tetrakis(fluoroaryl)borate compound from thesolution.

Exemplary mixing methods of the tetrakis(fluoroaryl)borate compound withthe cationic compound generating compound include, but not limited to:

a method of mixing the tetrakis(fluoroaryl)borate compound and cationiccompound generating compound with the reaction solvent;

a method of mixing the cationic compound generating compound or asolution thereof with a solution of the tetrakis(fluoroaryl)boratecompound;

a method of mixing the tetrakis(fluoroaryl)borate compound or a solutionthereof with a solution of the cationic compound generating compound;etc. In case that the solution of the cationic compound generatingcompound is mixed with the solution of the tetrakis(fluoroaryl)boratecompound, and the solution of the tetrakis(fluoroaryl)borate compound ismixed with the solution of the cationic compound generating compound, itis preferable to drop the former to the latter.

A temperature and a time in the reaction of thetetrakis(fluoroaryl)borate compound with the cationic compoundgenerating compound, that is, the reaction conditions, are notespecially limited. In the process of the present invention, thereaction can proceed readily by stirring a reaction liquid, prepared bydissolving the tetrakis(fluoroaryl)borate compound and the cationiccompound generating compound into the reaction solvent, for a certaintime at room temperature. Thus, the object product, that is, thetetrakis(fluoroaryl)borate derivative, can be readily obtained.

For example, when the tetrakis(fluoroaryl)borate compound is the alkalimetal salts or alkaline earth metal salts of tetrakis(fluoroaryl)borateand the cationic compound generating compound isN,N-dimethylaniline.hydrochloride, the object product, that is,N,N-dimethyl anilinium.tetrakis(fluoroaryl)borate can be obtained byreacting the above two compounds with each other, while alkali metalchloride, such as sodium chloride, or alkaline earth metal chloride,such as calcium chloride, is produced as a by-product. The alkali metalchloride or alkaline earth metal chloride can be readilyseparated/removed from the solution of N,N-dimethylanilinium.tetrakis(fluoroaryl)borate through the manipulation, such asliquid separation, filtration, and washing.

For example, when the tetrakis(fluoroaryl)borate compound is a hydrogencompound of tetrakis(fluoroaryl)borate and the cation seed generatingcompound is N,N-dimethylaniline.hydrochloride, the object product, thatis, N,N-dimethyl anilinium.tetrakis(fluoroaryl)borate can be obtained byreacting the above two compounds with each other, while hydrochloricacid is produced as a by-product. The hydrochloric acid can be readilyseparated/removed from N,N-dimethyl anilinium.tetrakis(fluoroaryl)boratethrough the manipulation, such as liquid separation and washing.

In short, the tetrakis(fluoroaryl)borate derivative can be readilyisolated/purified as crystals through an optional simple manipulation,such as removal (distillation) of the reaction solvent, after a simplemanipulation, such as liquid separation and filtration.

As has been explained, the process of producing thetetrakis(fluoroaryl)borate derivative of the present invention is aprocess of reacting the tetrakis(fluoroaryl)borate compound obtained byany of the above purifying processes with the cationic compoundgenerating compound.

According to the above process, the tetrakis(fluoroaryl)boratederivative can be produced efficiently at low costs from thetetrakis(fluoroaryl)borate compound, namely, alkali metal salts,alkaline earth metal salts, and hydrogen compound oftetrakis(fluoroaryl)borate. Since the resulting derivative does notcontain the impurities, such as magnesium halide, the derivative is sopure that it can be suitably used as a co-catalyst of the metallocenecatalyst used in the cationic complex polymerization reaction or aphotopolymeric catalyst for silicone.

A producing process of the tetrakis(fluoroaryl)borate.ether complex ofthe present invention is a process of reactingtetrakis(fluoroaryl)borate expressed by General Formula (5) above withthe ether compound expressed by General Formula (6) above. Consequently,the tetrakis(fluoroaryl)borate.ether complex of the present inventionexpressed by General Formula (4) above can be obtained.

Tetrakis(fluoroaryl)borate expressed by General Formula (5) above andused in the above process is a compound, in which each of thesubstituents denoted as R₁-R₁₀ is a hydrogen atom, fluorine atom, ahydrocarbon group or an alkoxy group, provided that at least one of thesubstituents denoted as R₁-R₅ is a fluorine atom and at least one of thesubstituents denoted as R₆-R₁₀ is a fluorine atom, a substituent denotedas M is a hydrogen atom, alkali metal, alkaline earth metal, or alkalineearth metal halide, n is 2 or 3, and m is 1 when M is a hydrogen atom,alkali metal, or alkaline earth metal halide, and 2 when M is alkalineearth metal. Examples of alkaline earth metal halide include magnesiumchloride, magnesium bromide, magnesium iodide, etc.

In other words, tetrakis(fluoroaryl)borate expressed by General Formula(5) above includes both the tetrakis(fluoroaryl)borate compoundexpressed by General Formula (3) above andtetrakis(fluoroaryl)borate.magnesium halide expressed by General Formula(1) above.

Of all the examples of tetrakis(fluoroaryl)borate expressed by Formula(5) above, tetrakis(pentafluorophenyl)borate.magnesium bromide,tetrakis(pentafluorophenyl)borate.lithium,tetrakis(pentafluorophenyl)borate.sodium, andtetrakis(pentafluorophenyl)borate.potassium are particularly preferred.Note that a process of producing tetrakis(fluoroaryl)borate is notlimited to the above disclosure.

The ether compound expressed by Formula (6) above and used in theprocess of the present invention is a compound, in which each of thesubstituents denoted as R₁₁l and R₁₂ is a hydrocarbon group which mayinclude a substituent containing a hetero atom, and a substituentdenoted as Y is a bivalent hydrocarbon group.

Examples of the hydrocarbon group include an alkyl group, an aryl group,a cycloalkyl group, a benzyl group, etc. However, an alkyl group havingup to 10 carbon atoms and an aryl group are particularly preferred.Examples of the substituent containing a hetero atom include:

substituents containing oxygen atoms, such as an alkoxy group, anaryloxy group, a cycloalkyloxy group, and an acyloxy group;

substituents containing nitrogen atoms, such as a dialkyl amino group;

substituents containing sulfur atoms, such as an alkylthio group and anarylthio group; etc.

The hydrocarbon bivalent group is preferably a bivalent group selectedfrom the group consisting of an alkylene group having up to six carbonatoms as a carbon chain linking two oxygen atoms, namely, a methylenegroup possibly having a substituent, an ethylene group possibly having asubstituent, a trimethylene group possibly having a substituent, atetramethylene group possibly having a substituent, a pentamethylenegroup possibly having a substituent, and a hexamethylene group possiblyhaving a substituent. It is more preferable that the substituent in thebivalent group is an alkyl group having up to six carbon atoms.

Examples of the ether compound expressed by General Formula (6) above(hereinafter, referred to as polyfunctional ether) include:

ethylene glycol dialkyl ether, such as 1,2-dimethoxy ethane,1,2-diethoxy ethane, ethylene glycol di-n-propyl ether, ethylene glycoldiisopropyl ether, ethylene glycol di-n-butyl ether, ethylene glycoldilsobutyl ether, ethylene glycol di-sec-butyl ether, ethylene glycoldi-t-butyl ether, ethylene glycol dipentyl ether, ethylene glycoldineopentyl ether, ethylene glycol dihexyl ether, ethylene glycoldiheptyl ether, ethylene glycol dioctyl ether, ethylene glycol dinonylether, and ethylene glycol didecyl ether;

ethylene glycol dicycloalkyl ether, such as ethylene glycoldicyclopropyl ether, ethylene glycol dicyclo butyl ether, ethyleneglycol dicyclopentyl ether, ethylene glycol dicyclohexyl ether, ethyleneglycol diheptyl ether, ethylene glycol dicyclo octyl ether, ethyleneglycol dicyclo nonyl ether, and ethylene glycol dicyclo decyl ether;

unsymetric ethylene glycol methyl alkyl ether, such as ethylene glycolmethyl ethyl ether, ethylene glycol methyl isopropyl ether, and ethyleneglycol methyl butyl ether;

diethylene glycol dialkyl ether, such as diethylene glycol dimethylether, diethylene glycol diethyl ether, diethylene glycol diisopropylether, diethylene glycol dibutyl ether, diethylene glycol dipentylether, diethylene glycol dihexyl ether, diethylene glycol diheptylether, diethylene glycol dioctyl ether, diethylene glycol dinonyl ether,and diethylene glycol didecyl ether;

triethylene glycol dialkyl ether, such as triethylene glycol dimethylether, triethylene glycol diethyl ether, triethylene glycol diisopropylether, triethylene glycol dibutyl ether, triethylene glycol dipentylether, triethylene glycol dihexyl ether, triethylene glycol diheptylether, triethylene glycol dioctyl ether, triethylene glycol dinonylether, and triethylene glycol didecyl ether;

ethylene glycol dialkyl ether having an acyloxy group, such asdiethylene glycol monoethyl ether acetate and diethylene glycolmonoethyl ether methacrylate;

ethylene glycol dialkyl ether having an alkylthio group, such asethylene glycol, di-2-methylthio ethyl ether;

ethylene glycol dialkyl ether having a dialkyl amino group, such asethylene glycol di-2-dimethyl amino ethyl ether;

ethylene glycol diaryl ether, such as ethylene glycol diphenyl ether;

diethylene glycol diaryl ether, such as diethylene glycol diphenylether;

triethylene glycol diaryl ether, such as triethylene glycol diphenylether;

ethylene glycol dibenzyl ether; etc.

It is preferable that the polyfunctional ether is in the state of liquidat room temperature. However, even if the polyfunctional ether is in thestate of solid at room temperature, it can be melted into a liquid withheating. Of all these example compounds, 1,2-dimethoxy ethane,1,2-diethoxy ethane, and diethylene glycol dimethyl ether areparticularly preferred because they can be readily converted intohighly-pure tetrakis(fluoroaryl)borate through distillation; moreover,they are inexpensive and readily available for industrial use.

The amount of polyfunctional ether used is not especially limited, butit is preferable to use a mole equivalent of polyfunctional ether totetrakis(fluoroaryl)borate, because tetrakis(fluoroaryl)borate and thepolyfunctional ether form the complex when their mole ratio is 1:1 orgreater. In the process of producing thetetrakis(fluoroaryl)borate.ether complex of the present invention, amethod of reacting tetrakis(fluoroaryl)borate with the polyfunctionalether is not especially limited, but a method of mixingtetrakis(fluoroaryl)borate with the polyfunctional ether in a solvent issuitable.

The solvent used in the above reaction can be any solvent generally usedfor organic synthesis, and is not especially limited. Examples of thesolvent include: organic solvents, such as aliphatic hydrocarbonsolvents, alicyclic hydrocarbon solvents, alcohol solvents, ketonesolvents, ester solvents, aromatic hydrocarbon solvents, and ethersolvents; water; etc. One member or a mixture of two or more membersselected from these example solvents can be used effectively.

Of all these example solvents, particularly preferred are the solventswith which the solubility of the tetrakis(fluoroaryl)borate.ethercomplex is relatively low, namely:

ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether,and anisole;

aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane;

alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane;

ester solvents, such as methyl acetate and ethyl acetate;

aromatic hydrocarbon solvents, such as benzene and toluene; etc.

When these solvents are used, the tetrakis(fluoroaryl)borate.ethercomplex can be readily crystallized and therefore, readily separatedfrom the solution.

When the solvents with which the solubility of thetetrakis(fluoroaryl)borate.ether complex is high, for example, alcoholsolvents, such as methyl alcohol and ethyl alcohol or ketone solvents,such as acetone and methyl ethyl ketone, are used, thetetrakis(fluoroaryl)borate.ether complex does not crystalize after theformation. Thus, in this case, the solvent is distilled out. Note thatpolar solvents, such as nitromethane and acetonitrile, are notpreferable, because they have higher coordination strength than thepolyfunctional ethers and inhibit the formation of the ether complex.

An amount of used solvent is not especially limited, but when thetetrakis(fluoroaryl)borate.ether complex alone is crystallized and takenout from the reaction series, it is preferable to use the solventsufficiently, so that tetrakis(fluoroaryl)borate is dissolved thereincompletely. Consequently, when the complex is formed usingtetrakis(fluoroaryl)borate containing a coloring component or by-productsalts, the coloring component or by-product salts remain in the reactionseries, and for this reason, a highly-pure colorlesstetrakis(fluoroaryl)borate.ether complex can be obtained through themanipulation, such as filtration.

An amount of used solvent does not have to be sufficient to dissolvetetrakis(fluroaryl)borate completely. For example, the complex can beformed if the reaction takes place in the suspended state. In this case,tetrakis(fluoroaryl)borate is reacted with the polyfunctional ether inthe suspended state, and the resulting tetrakis(fluoroaryl)borate.ethercomplex is taken out from the reaction series through filtration or thelike. In case that the tetrakis(fluoroaryl)borate.ether complex thustaken out contains the impurities, such as the coloring component andby-product salts, it is preferable to wash thetetrakis(fluoroaryl)borate.ether complex with an adequate solvent (forexample, ether solvents) that can dissolve these impurities.Consequently, a highly-pure colorless tetrakis (fluoroaryl)borate.ethercomplex can be obtained.

Alternatively, after the tetrakis(fluoroaryl)borate.ether complex isformed by reacting tetrakis(fluoroaryl)borate with excessivepolyfunctional ether without using the solvent, the excessivepolyfunctional ether that does not form the complex may be distilledout. In case that the resulting product contains the impurities, such asthe coloring component and by-product salts, it is preferable to washthe resulting product with an adequate solvent (for example, ethersolvents) which can dissolve these impurities.

A method of mixing tetrakis(fluoroaryl)borate with the polyfunctionalether and a mixing order thereof are not especially limited. Examplemixing methods are: a method of adding the polyfunctional ether to asolution of tetrakis(fluoroaryl)borate; a method of adding a solution oftetrakis(fluoroaryl)borate to the polyfunctional ether; etc.

The reaction temperature is not especially limited, but it is preferablyat or below the boiling point of the polyfunctional ether. When thesolvent is additionally used, it is further preferable that the reactiontemperature is at or below the boiling point of the solvent.

The reaction of tetrakis(fluoroaryl)borate and the polyfunctional ethertakes place very fast in a mixed rate-determining manner, but a time isrequired for the formed complex to grow to crystals. Thus, the reactiontime can be set to at least as long as the time necessary for the formedcomplex to grow to crystals. Further, the reaction can take place undernormal, reduced, or applied pressure.

The tetrakis(fluoroaryl)borate.ether complex can be obtained by theabove process. In case that the resultingtetrakis(fluoroaryl)borate.ether complex contains the impurities, suchas the coloring component and by-product salts, the resulting complexcan be readily purified to a high level when washed with an adequatesolvent (for example, ether solvent) that dissolves these impurities.Hence, the complex can be used as an excellent starting material of thetetrakis(fluoroaryl)borate derivative.

A process of producing the tetrakis(fluoroaryl)borate derivative of thepresent invention expressed by General Formula (2) above is a process,in which both the tetrakis(fluoroaryl)borate.ether complex and theaforementioned cationic compound generating compound are used as thestarting material. Also, the above process includes a step of removingthe polyfunctional ether from the reaction series. In the aboveproducing process, the tetrakis(fluoroaryl)borate.ether complex ortetrakis(fluoroaryl)borate is reacted with the cationic compoundgenerating compound in the aforementioned reaction solvent.

In other words, a process of producing the tetrakis(fluoroaryl)boratederivative of the present invention includes two types of processes:

a first process, in which, after tetrakis(fluoroaryl)borate is obtainedby removing the polyfunctional ether from thetetrakis(fluoroaryl)borate.ether complex, the resultingtetrakis(fluoroaryl)borate is reacted with the cationic compoundgenerating compound;

a second process, in which, after the tetrakis(fluoroaryl)boratederivative.ether complex is obtained by reacting thetetrakis(fluoroaryl)borate.ether complex with the cationic compoundgenerating compound, the polyfunctional ether is removed from theresulting tetrakis(fluoroaryl)borate derivative.ether complex.

In the first process, it is preferable that a first step of removing thepolyfunctional ether from the tetrakis(fluoroaryl)borate.ether complexis carried out by heating the tetrakis(fluoroaryl)borate.ether complexin a reaction vessel, so that the polyfunctional ether is distilled outfrom the reaction vessel.

The heating temperature is not especially limited as long as thepolyfunctional ether can be removed from thetetrakis(fluoroaryl)borate.ether complex. However, a preferabletemperature is 40° C. or above, and a range between 40° C. and 200° C.is further preferable. A heating time is not especially limited, either.

To distill out the polyfunctional ether from the reaction vessel, thetemperature inside the reaction vessel must be raised higher than theboiling point of the polyfunctional ether under the current pressureinside the reaction vessel. Thus, the pressure inside the reactionvessel may be reduced optionally. Consequently, the polyfunctional ethercan be distilled out at a relatively low temperature.

Also, in the first step, the tetrakis(fluoroaryl)borate.ether complexcan be in the form of a solution dissolved into the solvent, orsuspended in the solvent.

In the first producing process, if the first step of removing thepolyfunctional ether from the tetrakis(fluoroaryl)borate.ether complexis carried out solely, in other words, if a second step is not carriedout, the producing process is same as the producing process oftetrakis(fluoroaryl)borate. According to the above process, inexpensiveand highly-pure tetrakis(fluoroaryl)borate can be produced efficiently.

In the first process, the second step of reacting the resultingtetrakis(fluoroaryl)borate with the cationic compound generatingcompound is carried out in the aforementioned reaction solvent.

In case that the reaction is carried out using a solution oftetrakis(fluoroaryl)borate, a solution in whichtetrakis(fluoroaryl)borate is dissolved can be used as the reactionsolvent (either entirely or partially). Thus, thetetrakis(fluoroaryl)borate derivative can be produced using the solutionof the tetrakis(fluoroaryl)borate obtained in the first step withoutisolating the compound from the solution.

A method of mixing tetrakis(fluoroaryl)borate with the cationic compoundgenerating compound is not especially limited, and examples of whichare: a method of mixing tetrakis(fluoroaryl)borate and the cation seedgenerating compound with the reaction solvent; a method of mixing thecationic compound generating compound or a solution thereof with asolution of tetrakis(fluoroaryl)borate; a method of mixingtetrakis(fluoroaryl)borate or a solution thereof with a solution of thecationic compound generating compound; etc. In case that the solution ofthe cationic compound generating compound is mixed with the solution oftetrakis(fluoroaryl)borate, and the solution oftetrakis(fluoroaryl)borate is mixed with the solution of the cationiccompound generating compound, it is preferable to drop the former to thelatter.

A reaction temperature and a reaction time in the reaction oftetrakis(fluoroaryl)borate and the cationic compound generatingcompound, that is, the reaction conditions, are not especially limited.In the producing process of the present invention, the reaction isallowed to readily proceed by stirring a reaction liquid, prepared bydissolving tetrakis(fluoroaryl)borate and the cationic compoundgenerating compound into the reaction solvent, for a certain time atroom temperature. Consequently, the object product, that is, thetetrakis(fluoroaryl)borate derivative, can be readily obtained.

For example, when the tetrakis(fluoroaryl)borate is alkali metal saltsor alkaline earth metal salts of tetrakis(fluoroaryl)borate, and thecationic compound generating compound isN,N-dimethylaniline.hydrochloride, the object product, that is,N,N-dimethyl anilinium.tetrakis(fluoroaryl)borate, can be obtained byreacting the above two compounds with each other, while alkali metalchloride, such as sodium chloride, or alkaline earth metal chloride,such as calcium chloride, is produced as a by-product. The alkali metalchloride or alkaline earth metal chloride can be readilyseparated/removed from the solution of N,N-dimethylanilinium.tetrakis(fluoroaryl)borate through the manipulation, such asliquid separation, filtration, and washing. When the reaction solvent iswater, the alkali metal chloride or alkaline earth metal chloride can bereadily removed by filtering N,N-dimethylanilinium.tetrakis(fluoroaryl)borate followed by the washing with water.

Also, for example, when the tetrakis(fluoroaryl)borate istetrakis(fluoroaryl)borate.magnesium halide, and the cationic compoundgenerating compound is N,N-dimethylaniline.hydrochloride, the objectproduct, that is, N,N-dimethyl anilinium.tetrakis(fluoroaryl)borate, canbe obtained by reacting the above two compounds with each other, whilemagnesium halide, such as magnesium bromide chloride, is produced as aby-product.

The magnesium halide can be readily separated/removed from N,N-dimethylanilinium.tetrakis(fluoroaryl)borate through the manipulation, such asliquid separation, filtration, and washing. To be more specific,magnesium bromide chloride can be readily separated/removed by beingwashed with an acidic aqueous solution, such as hydrochloric acid, orbeing reacted with N,N-dimethylaniline hydrochloride containingexcessive hydrochloric acid followed by the washing with water.

In the second Process, a first step of reacting thetetrakis(fluoroaryl)borate.ether complex with the cationic compoundgenerating compound is carried out in the aforementioned reactionsolvent.

In the second producing Process, a first step of reacting thetetrakis(fluoroaryl)borate.ether complex with the cation seed generatingcompound is carried out in the aforementioned reaction solvent.

A method of mixing the tetrakis(fluoroaryl)borate.ether complex with thecationic compound generating compound is not especially limited, andexamples of which are: a method of mixing thetetrakis(fluoroaryl)borate.ether complex and the cationic compoundgenerating compound with the reaction solvent; a method of mixing thecationic compound generating compound or a solution thereof with asolution of the tetrakis(fluoroaryl)borate.ether complex; a method ofmixing the tetrakis(fluoroaryl)borate.ether complex or a solutionthereof with a solution of the cationic compound generating compound;etc. In case that the solution of the cationic compound generatingcompound is mixed with the solution of thetetrakis(fluoroaryl)borate.ether complex, and the solution of thetetrakis(fluoroaryl)borate.ether complex is mixed with the solution ofthe cationic compound generating compound, it is preferable to drop theformer to the latter.

A reaction temperature and a reaction time in the reaction of thetetrakis(fluoroaryl)borate.ether complex and the cationic compoundgenerating compound, that is, the reaction conditions, are notespecially limited. In the producing process of the present invention,the reaction is allowed to readily proceed by stirring a reaction liquidmade by dissolving or suspending the tetrakis(fluoroaryl)borate.ethercomplex and the cationic compound generating compound into the reactionsolvent for a certain time at or below the boiling point. Consequently,the object product, that is, the tetrakis(fluoroaryl)boratederivative.ether complex, can be readily obtained.

For example, when the tetrakis(fluoroaryl)borate.ether complex is atetrakis(fluoroaryl)borate.alkali metal salts.ether complex or atetrakis(fluoroaryl)borate.alkaline earth metal salts.ether complex, andthe generating compound is N,N-dimethylaniline.hydrochloride, the objectproduct, that is, N,N-dimethylanilinium.tetrakis(fluoroaryl)borate.ether complex, can be obtained byreacting the above two compounds with each other, while alkali metalchloride, such as sodium chloride, or alkaline earth metal chloride,such as calcium chloride, is produced as a by-product. The alkali metalchloride or alkaline earth metal chloride can be readilyseparated/removed from a solution of N,N-dimethylanilinium.tetrakis(fluoroaryl)borate.ether complex through themanipulation, such as liquid separation, filtration, and washing. Morespecifically, the alkali metal chloride can be separated/removed readilyby being washed with water.

Also, for example, when the tetrakis(fluoroaryl)borate.ether complex istetrakis(fluoroaryl)borate.magnesium halide-ether complex, and thecationic compound generating compound isN,N-dimethylaniline.hydrochloride, the object product, that is,N,N-dimethyl anilinium.tetrakis(fluoroaryl)borate.ether complex, can beobtained by reacting the above two compounds with each other, whilemagnesium halide, such as magnesium bromide chloride, is produced as aby-product.

The magnesium halide can be readily separated/removed from theN,N-dimethyl anilinium.tetrakis(fluoroaryl)borate.ether complex throughthe manipulation, such as liquid separation, filtration, and washing.More specifically, for example, magnesium bromide chloride can bereadily separated/removed by being washed with an acidic aqueoussolution, such as hydrochloric acid, or being, reacted withN,N-dimethylaniline.hydrochloride containing excessive hydrochloric acidfollowed by the washing with water.

In short, the tetrakis(fluoroaryl)borate derivative.ether complex can bereadily isolated/purified as crystals through an optional simplemanipulation, such as removal (distillation) of the reaction solvent orthe like after a simple manipulation, such as liquid separation andfiltration.

In the second process, if the first step of reacting the cationiccompound generating compound is carried out solely, in other words, if asecond step is not carried out, it is same as the process of thetetrakis(fluoroaryl)borate derivative.ether complex. According to theabove process, an inexpensive and highly-pure tetrakis(fluoroaryl)boratederivative.ether complex, which is useful as an intermediate forproducing the tetrakis(fluoroaryl)borate derivative, can be producedefficiently.

In the second producing process, it is preferable to carry out thesecond step of removing the polyfunctional ether from thetetrakis(fluoroaryl)borate derivative.ether complex by heating thetetrakis(fluoroaryl)borate derivative.ether complex within a reactionvessel, so that the polyfunctional ether is distilled out from thereaction vessel.

The heating temperature is not especially limited as long as thepolyfunctional ether can be removed from the tetrakis(fluoroaryl)boratederivative.ether complex. However, a preferable temperature is 40° C. orabove, and a range between 40° C. and 200° C. is further preferable. Aheating time is not especially limited, either.

To distill out the polyfunctional ether from the reaction vessel, thetemperature inside the reaction vessel must be raised higher than theboiling point of the polyfunctional ether under the current pressureinside the reaction vessel. Thus, the pressure inside the reactionvessel may be reduced optionally. Consequently, the polyfunctional ethercan be distilled out at a relatively low temperature.

Also, in the second step, the tetrakis(fluoroaryl)boratederivative.ether complex can be in the form of a solution dissolved intothe solvent, or suspended in the solvent.

In case that the reaction is carried out using a solution of thetetrakis(fluoroaryl)borate derivative.ether complex, a solution in whichtetrakis(fluoroaryl)borate is dissolved can be used as the solvent(either entirely or partially). Thus, the tetrakis(fluoroaryl)boratederivative can be produced using the solution of thetetrakis(fluoroaryl)borate derivative.ether complex obtained in thefirst step without isolating the ether complex from the solution.

In the second producing process, if the second step of removing thepolyfunctional ether from the tetrakis(fluoroaryl)boratederivative.ether complex is carried out solely, in other words, if thefirst step is not carried out, the producing process is same as theproducing process of an inexpensive and highly-puretetrakis(fluoroaryl)borate derivative efficiently.

Other and further objects, features, and advantages of the presentinvention will appear more fully from the following description. Also;the benefits of the present invention will be apparent from the ensuingexplanation.

THE BEST MODE FOR IMPLEMENTING THE INVENTION

The present invention will be explained in detail by way of examples;however, the present invention is not limited to the followingdisclosure. In the following examples, NMR (Nuclear Magnetic Resonance)spectrum data are measured using tetramethyl silane (TMS) as a referencereagent in case of ¹H-NMR, and using trifluoro acetate as the referencereagent in case of ¹⁹F-NMR, by setting the signal of each referencereagent to 0 ppm.

EXAMPLE 1

Here, 100 ml of a mixed solution of diethyl ether and toluene containing0.0257 mol of tetrakis (pentafluorophenyl)borate.magnesium bromide astetrakis (fluoroaryl)borate.magnesium halide is charged to a reactionvessel equipped with a thermometer, a dropping funnel, a stirrer, and areflux condenser. A mixing volume ratio of diethyl ether and toluene asthe solvent is 1:1. The mixed solution contains 0.0771 mol of magnesiumbromide fluoride as the impurities. Meanwhile, 100 ml (0.100 mol) of anaqueous solution of sodium carbonate serving as the carboxylate ischarged to the dropping funnel.

Then, the aqueous solution is dropped to the mixed solution over 10minutes at room temperature with stirring of the mixed solution, and thereaction solution is stirred for further 30 minutes at room temperature.In other words, the purifying process {circle around (1)} of the presentinvention is adopted herein. When the stirring ends, the deposit(magnesium carbonate) is removed by subjecting the reaction solution tosuction filtration.

The filtrate is separated into an organic layer and a water layer, afterwhich the water layer is extracted twice using 50 ml of ethyl acetate ineach. Then, ethyl acetate (approximately 100 ml) used as the extractionliquid is added to the organic layer, while magnesium sulfate anhydrideserving as a drying agent is added to dry the same.

When the organic layer is dried, diethyl ether, toluene, and ethylacetate are distilled out from the organic layer under reduced pressure,whereby brown crystals of tetrakis(pentafluorophenyl)borate.sodium areobtained as the tetrakis(fluoroaryl)borate compound.

A survival rate of magnesium in the crystals is measured through X-rayfluorescence analysis, and no magnesium is detected in the crystals.Thus, it turned out that the crystals do not contain the impurities,such as magnesium halide.

Also, the yield of tetrakis(pentafluorophenyl)borate.sodium is found bymeasuring ¹⁹F-NMR. More specifically, ¹⁹F-NMR is measured underpredetermined conditions using p-fluorotoluene as an internal standardreagent. Then, a peak integral of a fluorine atom of p-fluorotoluene,and a peak integral of fluorine atoms at the ortho-position of apentafluorophenyl group in tetrakis(pentafluorophenyl)borate.sodium arecomputed from the resulting ¹⁹F-NMR chart first, and thence an amount oftetrakis(pentafluorophenyl)borate.sodium is computed using the above twopeak integrals. The yield and purity oftetrakis(pentafluorophenyl)borate.sodium thus found are 89.1 mol % and96.0%, respectively.

EXAMPLE 2

Here, 100 ml of a mixed solution of diethyl ether and toluene containing0.025 mol of tetrakis (pentafluorophenyl)borate.magnesium bromide ischarged to a reaction vessel of the same type as the one used inExample 1. A mixing volume ratio of diethyl ether and toluene is 1:1.Meanwhile, 100 ml (0.100 mol) of an aqueous solution of sodium acetateserving as the carboxylate is charged to the dropping funnel.

Then, the aqueous solution is dropped to the mixed solution over 10minutes at room temperature with stirring of the mixed solution, and thereaction solution is stirred for further 60 minutes at room temperature.In other words, the purifying process {circle around (1)} of the presentinvention is adopted. When the stirring ends, the resulting solution isseparated to an organic layer and a water layer, and the water later isextracted once using 50 ml of ethyl acetate. Subsequently, ethyl acetateserving as an extraction liquid is added to the organic layer, whilemagnesium sulfate anhydride is added to dry the same.

When the organic layer is dried, diethyl ether, toluene, and ethylacetate are distilled out from the organic layer under reduced pressure,whereby brown crystals of tetrakis(pentafluorophenyl)borate.sodium areobtained. The yield and purity oftetrakis(pentafluorophenyl)borate.sodium found in the same manner asExample 1 are 92.1 mol % and 97.4%, respectively.

EXAMPLE 3

Here, 160 ml of a solution (concentration: 29.5 mol %) of di-n-butylether containing 0.047 mol oftetrakis(pentafluorophenyl)borate.magnesium bromide, and 300 ml (0.300mol) of 1N-hydrochloric acid serving as the acid are charged to aseparatory funnel having a capacity of 500 ml. Then, the separatoryfunnel is shaken satisfactorily first, and thence allowed to stand,whereby the solution is separated to an organic layer and a water layer.In other words, the purifying process {circle around (2)} of the presentinvention is adopted. The organic layer thus obtained is dried with anaddition of magnesium sulfate anhydride.

When the organic layer is dried, di-n-butyl ether serving as the solventis distilled out from the organic layer under reduced pressure, wherebya hydrogen compound of tetrakis(pentafluorophenyl)borate. is obtained.The yield of the hydrogen compound of tetrakis(pentafluorophenyl)borate.found in the same manner as Example 1 is 89.7 mol %.

EXAMPLE 4

Here, 47.9 g of a solution (concentration: 38.7 mol %) of toluenecontaining 0.018 mol of tetrakis(pentafluorophenyl)borate.magnesiumbromide, and 160 ml (0.160 mol) of 1N-hydrochloric acid are charged to aseparatory funnel having a capacity of 300 ml. Then, the separatoryfunnel is shaken satisfactorily first, and thence allowed to stand,whereby the solution is separated to an organic layer and a water layer.

Then, the organic layer and 30 ml (0.030 mol) of an aqueous solution of1N-sodium hydroxide serving as the hydroxide are charged to a conicalflask equipped with a stirrer and having a capacity of 200 ml, and thereaction solution is stirred for one hour at room temperature. When thestirring ends, the solution is separated to an organic layer and a waterlayer. In other words, the purifying process {circle around (3)} of thepresent invention is adopted. The organic layer thus obtained is driedwith an addition of magnesium sulfate anhydride.

When the organic layer is dried, toluene is distilled out from theorganic layer under reduced pressure, whereby crystals oftetrakis(pentafluorophenyl)borate.sodium are obtained. The yield oftetrakis(pentafluorophenyl)borate.sodium found in the same manner asExample 1 is 93.5 mol %.

EXAMPLE 5

Here, 45.6 g of a solution (concentration: 37.4 mol %) of toluenecontaining 0.017 mol of tetrakis(pentafluorophenyl)borate.magnesiumbromide, and 75 ml (0.150 mol) of 0.5N-sulfuric acid serving as the acidare charged to a separatory funnel having a capacity of 300 ml. Then,the separatory funnel is shaken satisfactorily first, and thence allowedto stand, whereby the solution is separated to an organic layer and awater layer.

Then, the organic layer and 20 ml (0.020 mol) of an aqueous solution of1N-sodium hydroxide are charged to a conical flask equipped with astirrer and having a capacity of 200 ml, and the reaction solution isstirred for one hour at room temperature. When the stirring ends, thesolution is separated to an organic layer and a water layer. In otherwords, the purifying process {circle around (3)} of the presentinvention is adopted. The organic layer thus obtained is dried with anaddition of magnesium sulfate anhydride.

When the organic layer is dried, toluene is distilled out from theorganic layer under reduced pressure, whereby crystals oftetrakis(pentafluorophenyl)borate.sodium are obtained. The yield oftetrakis(pentafluorophenyl)borate.sodium found in the same manner asExample 1 is 91.5 mol %.

EXAMPLE 6

Here, 50 ml (0.100 mol) of an aqueous solution of oxalic acid serving asthe acid is charged to a reaction vessel of the same type as the oneused in Example 1. Meanwhile, 100 ml of a solution of di-n-butyl ethercontaining 0.025 mol of tetrakis(pentafluorophenyl)borate.magnesiumbromide is charged to the dropping funnel.

Then, the solution is dropped to the aqueous solution over 10 minutes atroom temperature with stirring of the aqueous solution, and the reactionsolution is stirred for further 60 minutes at room temperature. When thestirring ends, the resulting solution is separated to an organic layerand a water layer, after which the organic layer is washed with a 10 wt% aqueous solution of sodium hydroxide serving as the alkali metalhydroxide. Then, the washed solution is separated to an organic layerand a water layer. In other words, the purifying process {circle around(3)} of the present invention is adopted. The organic layer thusobtained is dried with an addition of magnesium sulfate anhydride.

When the organic layer is dried, di-n-butyl ether is distilled out fromthe organic layer under reduced pressure, whereby crystals oftetrakis(pentafluorophenyl)borate.sodium are obtained. The yield oftetrakis(pentafluorophenyl)borate.sodium found in the same manner asExample 1 is 95.0 mol %.

EXAMPLE 7

Here, 100 ml of a mixed solution of diethyl ether and di-n-butyl ethercontaining 0.042 mol of tetrakis (pentafluorophenyl)borate.magnesiumbromide is charged to a reaction vessel of the same type as the one usedin Example 1. A mixing volume ratio of diethyl ether and di-n-butylether as the solvent is 1:6. Meanwhile, 132 g of a 10 wt % aqueoussolution of hydrochloric acid is charged to the dropping funnel.

Then, the aqueous solution is dropped to the mixed solution over 10minutes at room temperature with stirring of the mixed solution, and thereaction solution is stirred for further 60 minutes at room temperature.When the stirring ends, the resulting solution is separated to anorganic layer and a water layer. The organic layer thus obtained iswashed with a 15 wt % aqueous solution of sodium succinate dibasicserving as the carboxylate, after which the solution is separated to anorganic layer and a water layer. In other words, the purifying process{circle around (4)} of the present invention is adopted. The organiclayer thus obtained is dried with an addition of magnesium sulfateanhydride.

When the organic layer is dried, diethyl ether and di-n-butyl ether aredistilled out from the organic layer under reduced pressure, wherebycrystals of tetrakis(pentafluorophenyl)borate.sodium are obtained. Theyield of tetrakis(pentafluorophenyl)borate.sodium found in the samemanner as Example 1 is 97.9 mol %.

EXAMPLE 8

Here, 100 ml of a mixed solution of diethyl ether and di-n-butyl ethercontaining 0.041 mol of tetrakis(pentafluorophenyl)borate.magnesiumbromide is charged to a reaction vessel of the same type as the one usedin Example 1. A mixing volume ratio of diethyl ether and di-n-butylether is 1:6. Meanwhile, 132 g of a 10 wt % aqueous solution ofhydrochloric acid is charged to the dropping funnel.

Then, the aqueous solution is dropped to the mixed solution over 10minutes at room temperature with stirring of the mixed solution, and thereaction solution is stirred for 60 minutes at room temperature. Whenthe stirring ends, the resulting solution is separated to an organiclayer and a water layer. The organic layer thus obtained is washed witha 10 wt % aqueous solution of sodium carbonate, after which the solutionis separated to an organic layer and a water layer. In other words, thepurifying process {circle around (4)} of the present invention isadopted. The organic layer thus obtained is dried with an addition ofmagnesium sulfate anhydride.

When the organic layer is dried, diethyl ether and di-n-butyl ether aredistilled out from the organic layer under reduced pressure, wherebycrystals of tetrakis(pentaflurorphenyl)borate.sodium are obtained. Theyield of tetrakis(pentafluorophenyl)borate.sodium found in the samemanner as Example 1 is 95.6 mol %.

EXAMPLE 9

Here, 16.1 g of tetrakis(pentafluorophenyl)borate.sodium obtained inExample 1 and 100 ml of ethyl acetate serving as the reaction solventare charged to a reaction vessel of the same type as the one used inExample 1. Meanwhile, 100 ml (0.025 mol) of an aqueous solution ofN,N-dimethylaniline.hydrochloride serving as the cation seed generatingcompound is charged to the dropping funnel.

Then, the aqueous solution is dropped to the solution over 10 minutes atroom temperature with stirring of the solution, and the reactionsolution is let undergo reaction for one hour at room temperature withstirring. When the reaction ends, the reaction solution is separated toan organic layer and a water layer, and the water layer is extractedonce using 50 ml of ethyl acetate. Then, ethyl acetate serving as anextraction liquid is added to the organic layer, while magnesium sulfateanhydride is added to dry the same.

When the organic layer is dried, ethyl acetate is distilled out from theorganic layer under reduced pressure, whereupon black crystals areobtained. The crystals are washed with 50 ml of diisopropyl ether,whereby light-brown N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate is obtained as thetetrakis(fluoroaryl)borate derivative. The yield of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate found in the same manner asExample 1, that is, by measuring ¹⁹F-NMR using p-fluorotoluene as theinternal standard reagent, is 89.9 mol %.

EXAMPLE 10

Here, 16.6 g of tetrakis(pentafluorophenyl)borate.sodium obtained inExample 2 and 100 ml of ethyl acetate are charged to a reaction vesselof the same type as the one used in Example 1. Meanwhile, 100 ml (0.025mol) of an aqueous solution of N,N-dimethylaniline.hydrochloride ischarged to the dropping funnel.

Then, the aqueous solution is dropped to the solution over 10 minutes atroom temperature with stirring of the solution, and the reactionsolution is let undergo reaction for one hour at room temperature withstirring. When the reaction ends, the reaction solution is separated toan organic layer and a water layer, and the water layer is extractedonce using 50 ml of ethyl acetate. Then, ethyl acetate serving as anextraction liquid is added to the organic layer, while magnesium sulfateanhydride is added to dry the same.

When the organic layer is dried, ethyl acetate is distilled out from theorganic layer under reduced pressure, whereupon brown crystals areobtained. The crystals are washed with 50 ml of diisopropyl ether,whereby light-gray N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate is obtained. The yield of N,N-dimethylanilinium.tetrakis(pentaflurophenyl)borate found in the same manner asExample 9 is 83.0 mol %.

EXAMPLE 11

Here, 59.8 g of a solution (concentration: 35.7 mol %) of di-n-butylether containing 0.021 mol oftetrakis(pentafluorophenyl)borate.magnesium bromide and 250 ml (0.250mol) of 1N-formic acid serving as the acid are charged to a separatoryfunnel having a capacity of 500 ml. Then, the separatory funnel isshaken satisfactorily first, and thence allowed to stand, whereby thesolution is separated to an organic layer and a water layer. After thewater layer is taken out, 70 ml (0.014 mol) of an aqueous solution of2N-lithium hydroxide serving as the hydroxide is added to the organiclayer. Then, the separatory funnel is shaken satisfactorily again, andsubsequently allowed to stand, whereby the solution is separated to anorganic layer and a water layer. In other words, the purifying process{circle around (3)} of the present invention is adopted. Then, magnesiumsulfate anhydride is added to the organic layer to dry the same.

Subsequently, the organic layer is charged to a 4-neck flask equippedwith a thermometer, a dropping funnel, a stirrer, and a refluxcondenser, and having a capacity of 200 ml. Meanwhile, 2.84 g (0.023mol) of N,N-dimethylaniline serving as the cation seed generatingcompound is charged to the dropping funnel.

Then, N,N-dimethylaniline is dropped to the organic layer over 15minutes at room temperature with stirring of the organic layer, and thereaction solution is let undergo reaction for one hour at roomtemperature with stirring. When the reaction ends, di-n-butyl ether isdistilled out from the organic layer under reduced pressure, wherebyN,N-dimethyl anilinium.tetrakis (pentafluorophenyl)borate is obtained.The yield of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)boratefound in the same manner as Example 9 is 91.2 mol %.

EXAMPLE 12

Here, 80 ml of a solution (concentration: 29.5 mol %) of di-n-butylether containing 0.023 mol oftetrakis(pentafluorophenyl)borate.magnesium bromide, and 150 ml (0.150mol) of 1N-hydrochloric acid are charged to a separatory funnel having acapacity of 500 ml. Then, the separatory funnel is shaken satisfactorilyfirst, and thence allowed to stand, whereby the solution is separated toan organic layer and a water layer. After the water layer is taken out,33.0 ml (0.031 mol) of a 10 wt % aqueous solution of sodium carbonate isadded to the organic layer. Then, the separatory funnel is shakensatisfactorily again, and subsequently allowed to stand, whereby thesolution is separated to an organic layer and a water layer. In otherwords, the purifying process {circle around (4)} of the presentinvention is adopted. Then, magnesium sulfate anhydride is added to theorganic layer to dry the same.

Then, the organic layer and 3.72 g (0.024 mol) ofN,N-dimethylaniline.hydrochloride are charged to a 4-neck flask equippedwith a thermometer, a stirrer, and a reflux condenser and having acapacity of 200 ml. Then, the organic layer is let undergo reaction forone hour at room temperature with stirring. When the reaction ends,di-n-butyl ether is distilled out from the organic layer under reducedpressure, whereby N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate is obtained. The yield ofN,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate found in thesame manner as Example 9 is 86.7 mol %.

EXAMPLE 13

The reaction and manipulation are carried out in the same manner asExample 12 except that 83.0 ml (0.031 mol) of a 20 wt % aqueous solutionof sodium succinate dibasic is charged instead of 33.0 ml of the 10 wt %aqueous solution of sodium carbonate; and that an amount of usedN,N-dimethylaniline.hydrochloride is increased to 3.99 g (0.025 mol)from 3.72 g (0.024 mol), whereby N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate is obtained. The yield ofN,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate found in thesame manner as Example 9 is 87.3 mol %.

EXAMPLE 14

Here, 50.0 g of a solution of di-n-butyl ether containing 0.016 mol oftetrakis(pentafluorophenyl)borate.magnesium bromide, and 140 ml of1N-hydrochloride are charged to a separatory funnel having a capacity of500 ml. Then, the separatory funnel is shaken satisfactorily first, andthence allowed to stand, whereby the solution is separated to an organiclayer and a water layer. In other words, the purifying process {circlearound (2)} of the present invention is adopted. Then, magnesium sulfateanhydride is added to the organic layer to dry the same.

Subsequently, the organic layer is charged to a 4-neck flask equippedwith a thermometer, a dropping funnel, a stirrer, and a reflux condenserand having a capacity of 200 ml. Meanwhile, 2.06 g (0.017 mol) ofN,N-dimethylaniline is charged to the dropping funnel.

Then, N,N-dimethylaniline is dropped to the organic layer over 10minutes at room temperature with stirring of the organic layer, and thereaction solution is let undergo reaction for one hour at roomtemperature with stirring. When the reaction ends, di-n-butyl ether isdistilled out from the organic layer under reduced pressure, whereby N,N-dimethyl anilinium.tetrakis (pentafluorophenyl)borate is obtained. Theyield of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate foundin the same manner as Example 9 is 94.8 mol %.

EXAMPLE 15

Here, 130.6 g of a solution (concentration: 15.8 mol %) of di-n-butylether containing 0.021 mol oftetrakis(pentafluorophenyl)borate.magnesium bromide and 180 ml (0.180mol) of 1N-sulfuric acid serving as the acid are charged to a separatoryfunnel having a capacity of 500 ml. Then, the separatory funnel isshaken satisfactorily first, and thence allowed to stand, whereby thesolution is separated to an organic layer and a water layer. In otherwords, the purifying process {circle around (2)} of the presentinvention is adopted. Then, magnesium sulfate anhydride is added to theorganic layer to dry the same.

Subsequently, the organic layer is charged to a 4-neck flask equippedwith a thermometer, a dropping funnel, a stirrer, and a reflux condenserand having a capacity of 200 ml. Meanwhile, 2.74 g (0.027 mol) ofN,N-dimethylaniline is charged to the dropping funnel.

Then, N,N-dimethylaniline is dropped to the organic layer over 15minutes at room temperature with stirring of the organic layer, and thereaction solution is let undergo reaction for one hour at roomtemperature with stirring. When the reaction ends, di-n-butyl ether isdistilled out from the organic layer under reduced pressure, wherebyN,N-dimethyl anilinium.tetrakis (pentafluorophenyl)borate is obtained.The yield of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)boratefound in the same manner as Example 9 is 90.3 mol %.

EXAMPLE 16

Here, 120.7 g of a solution (concentration: 16.6 mol %) of di-n-butylether containing 0.020 mol oftetrakis(pentafluorophenyl)borate.magnesium bromide and 90 ml (0.180mol) of 2N-formic acid are charged to a separatory funnel having acapacity of 500 ml. Then, the separatory funnel is shaken satisfactorilyfirst, and thence allowed to stand, whereby the solution is separated toan organic layer and a water layer. In other words, the purifyingprocess {circle around (2)} of the present invention is adopted. Then,magnesium sulfate anhydride is added to the organic layer to dry thesame.

Subsequently, the organic layer is charged to a 4-neck flask equippedwith a thermometer, a dropping funnel, a stirrer, and a reflux condenserand having a capacity of 200 ml. Meanwhile, 2.62 g (0.022 mol) ofN,N-dimethylaniline is charged to the dropping funnel.

Then, N,N-dimethylaniline is dropped to the organic layer over 15minutes at room temperature with stirring of the organic layer, and thereaction solution is let undergo reaction for one hour at roomtemperature with stirring. When the reaction ends, di-n-butyl ether isdistilled out from the organic layer under reduced pressure, wherebyN,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate is obtained.The yield of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)boratefound in the same manner as Example 9 is 89.6 mol %.

EXAMPLE 17

Here, 200 ml of a solution of di-n-butyl ether containing 0.045 mol oftetrakis(pentafluorophenyl)borate.lithium serving astetrakis(fluoroaryl)borate is charged to a reaction vessel equipped witha thermometer, a dropping funnel, a reflux condenser, and a stirrer.Meanwhile, 0.45 mol of 1,2-dimethoxy ethane serving as thepolyfunctional ether is charged to the dropping funnel.

Then, 1,2-dimethoxy ethane in the dropping funnel is dropped to thecontent in the reaction vessel over 10 minutes at room temperature withstirring of the content, and the reaction solution is stirred forfurther 30 minutes at the same temperature (room temperature), wherebythe reaction solution is crystallized. The resulting crystals arecollected by subjecting the content in the reaction vessel to thesuction filtration, and then washed with 20 ml of isopropyl ether.

The crystals thus obtained are dried under reduced pressure, wherebywhite crystals of atetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethane complexis obtained as the tetrakis(fluoroaryl)borate.polyfunctional ethercomplex.

The yield of the tetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxyethane complex is found by measuring ¹⁹F-NMR (Nuclear MagneticResonance) spectrum. In other words, ¹⁹F-NMR is measured underpredetermined conditions using p-fluorotoluene as the internal standardreagent. Then, a ratio of a peak integral of a fluorine atom ofp-fluorotoluene, and a peak integral of fluorine atoms at theortho-position of a pentafluorophenyl group in thetetrakis(pentafluorophenyl)borate.lithium. 1,2-dimethoxy ethane complexis computed from the resulting ¹⁹F-NMR chart first, and thence a weightof the tetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethanecomplex is computed using the above peak integral ratio.

The yield of the tetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxyethane complex with respect to tetrakis(pentafluorophenyl)borate.lithiumthus found is 85.2 mol %, and the purity of thetetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethane complexthus found is 99%.

Further, ¹H-NMR is measured under predetermined conditions usingp-fluorotoluene as the internal standard reagent. Then, a ratio of apeak integral of a methyl group of p-fluorotoluene, and a peak integralof methyl groups of 1,2-dimethoxy ethane is computed from the resulting¹H-NMR chart first, and thence a mol amount of 1,2-dimethoxy ethane iscomputed using the above peak integral ratio.

A mole ratio of tetrakis(pentafluorophenyl)borate.lithium and1,2-dimethoxy ethane in thetetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethane complexthus found is 1:2.

The tetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethanecomplex is identified through the analysis of the measured meltingpoint, IR (Infrared absorption spectrum), ¹⁹F-NMR, and ¹H-NRM, as wellas the elemental analysis. Here, given the following as the dataobtained through the analysis,

melting point: 119° C.-120° C. IR (KBr, cm⁻¹): 2947, 1642, 1515, 1464,1279, 1121, 1083, 978, 868 ¹⁹F-NMR (CDCl₃, δ): −56.9, −87.1, −91.1¹H-NRM (CDCl₃, δ): 3.41 (6H, s), 3.57 (4H, s)

elemental analysis: C₂₄F₂₀Bli.2C₄H₁₀O₂ then, a computed value (%) is,

hydrogen: 2.33, carbon: 44.37, fluorine: 43.87 and an analysis value (%)is,

hydrogen: 2.47, carbon: 44.36, fluorine: 43.33.

EXAMPLE 18

Here, a mixed solution is prepared by dissolving 0.0214 mol oftetrakis(pentafluorophenyl)borate.sodium serving astetrakis(fluoroaryl)borate into a mixed solvent of diethyl ether anddi-n-butyl ether (volume ratio of diethyl ether and di-n-butyl ether:1:1), and 100 ml of which is charged to a reaction vessel of the sametype as the one used in Example 17. Meanwhile, 0.900 mol of1,2-dimethoxy, ethane is charged to the dropping funnel.

Then, 1,2-dimethoxy ethane in the dropping funnel is dropped to thecontent in the reaction vessel over 10 minutes at room temperature withstirring of the content, and the reaction solution is stirred forfurther 30 minutes at the same temperature (room temperature). Then,diethyl ether and excessive 1,2-dimethoxy ethane are distilled out fromthe reaction vessel under reduced pressure, whereby the reactionsolution is crystallized. The crystals are collected by subjecting thecontent in the reaction vessel to the suction filtration, and thenwashed with 100 ml of n-hexane.

Then, the washed crystals are dried under reduced pressure, wherebywhite-yellow crystals of atetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexare obtained as the tetrakis(fluoroaryl)borate polyfunctional ethercomplex.

The yield of the tetrakis(pentafluorophenyl) borate.sodium.1,2-dimethoxyethane complex with respect to the tetrakis(fluoroaryl)borate.sodium andthe purity of the tetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxyethane complex analyzed in the same manner as Example 17 are 95.7 mol %and 99%, respectively.

Also, a mole ratio of tetrakis(pentafluorophenyl)borate.sodium and1,2-dimethoxy ethane in thetetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complex is1:3.

The tetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethanecomplex is identified with the following analysis data. That is, given

melting point: 159° C.-162° C. IR (KBr, cm⁻¹): 2948, 2908, 1645, 1471,1278, 1128, 1087, 975, 860 ¹⁹F-NMR (CDCl₃, δ): −57.4, −86.8, −91.2¹H-NRM (CDCl₃, δ): 3.35 (6H, s), 3.53 (4H, s)

elemental analysis: C₂₄F₂₀BNa.3C₄H₁₀O₂ then, a computed value (%) is,

hydrogen: 3.06, carbon: 43.73, fluorine: 38.43 and an analysis value (%)is,

hydrogen: 3.03, carbon: 45.13, fluorine: 38.86.

EXAMPLE 19

Here, 200 ml of a solution of di-n-butyl ether containing 0.0414 mol oftetrakis(pentafluorophenyl)borate.potassium serving astetrakis(fluoroaryl)borate is charged to a reaction vessel of the sametype as the one used in Example 17. Meanwhile, 0.900 mol of1,2-dimethoxy ethane is charged to the dropping funnel.

Then, 1,2-dimethoxy ethane in the dropping funnel is dropped to thecontent in the reaction vessel over 10 minutes at room temperature withstirring of the content, and the reaction solution is stirred forfurther 30 minutes at the same temperature (room temperature). Then, thereaction solution is heated to 110° C. to distill out excessive1,2-dimethoxy ethane and subsequently cooled to room temperature,whereby the reaction solution is crystallized. The crystals arecollected by subjecting the content in the reaction vessel to thesuction filtration, and then washed with 100 ml of n-hexane. Then, thewashed crystals are dried under reduced pressure, whereby white-yellowpowders of a tetrakis(pentafluorophenyl)borate.potassium.1,2-dimethoxyethane complex are obtained as the tetrakis(fluoroaryl)borate.polyfunctional ether complex.

The yield and purity of the tetrakis (pentafluorophenyl)borate.potassium1,2-dimethoxy ethane complex analyzed in the same manner as Example 17are 71.5 mol % and 99%, respectively. Also, a mole ratio oftetrakis(pentafluorophenyl)borate.potassium and 1,2-dimethoxy ethane inthe tetrakis(pentafluorophenyl)borate.potassium.1,2-dimethoxy ethanecomplex is 1:3.

The tetrakis(pentafluorophenyl)borate.potassium.1,2-dimethoxy ethanecomplex is identified with the following analysis data. That is, given

melting point: 127° C.-130° C. IR (KBr, cm⁻¹): 2944, 2906, 1645, 1515,1466, 1277, 1125, 1087, 978, 857 ¹⁹F-NMR (CDCl₃, δ): −57.2, −86.7, −90.9¹H-NRM (CDCl₃, δ): 3.33 (6H, s), 3.51 (4H, s)

elemental analysis: C₂₄F₂₀BK.3 C₄H₁₀O₂ then, a computed value (%) is,

hydrogen: 3.08, carbon: 44.44, fluorine: 39.09 and an analysis value (%)is,

hydrogen: 3.07, carbon: 44.03, fluorine: 37.98.

EXAMPLE 20

Here, 0.0214 mol of tetrakis(pentafluorophenyl)borate.lithium issuspended in 50 ml of ion-exchange water in a reaction vessel of thesame type as the one used in Example 17, and the resulting suspendedliquid is heated to 50° C., so thattetrakis(pentafluorophenyl)borate.lithium is dissolved into theion-exchange water. Then, 50 ml of 1,2-diethoxy ethane serving as thepolyfunctional ether is added to the resulting solution, and thereaction solution is stirred for 10 minutes, whereby the reaction mixedsolution is separated to an organic layer and a water layer. The waterlayer is extracted using 50 ml of 1,2-diethoxy ethane and the organiclayer thus obtained is mixed with another organic layer which has beenseparated before.

The mixed organic layer is dried with magnesium sulfate anhydride, andsubsequently, the solvent (1,2-diethoxy ethane) is distilled out underreduced pressure, whereby brown crystals of atetrakis(pentafluorophenyl)borate.lithium.1,2-diethoxy ethane complexare obtained as the tetrakis(fluoroaryl)borate.polyfunctional ethercomplex.

The yield and purity of thetetrakis(pentafluorophenyl)borate.lithium.1,2-diethoxy ethane complexanalyzed in the same manner as Example 17 are 91.1 mol % and 99%,respectively. Also, a mole ratio oftetrakis(pentafluorophenyl)borate.lithium and 1,2-diethoxy ethane in thetetrakis(pentafluorophenyl)borate.lithium.1,2-diethoxy ethane complex is1:3.

The tetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethanecomplex is identified with the following analysis data,

melting point: 170° C.-172° C. IR (KBr, cm⁻¹): 2986, 2941, 1645, 1516,1465, 1276, 1119, 1084, 1066, 980 ¹⁹F-NMR (DMSO-d₆, δ): −56.8, −87.3,−91.1 ¹H-NRM (DMSO-d₆, δ): 1.24 (6H, t, J = 7.2 Hz), 3.66 (4H, q, J =7.2 Hz), 3.69 (4H, s).

EXAMPLE 21

Here, 0.010 mol of tetrakis(pentafluorophenyl)borate.sodium is suspendedin 50 ml of ion-exchange water in a reaction vessel of the same type asthe one used in Example 17, and 50 ml of 1,2-diethoxy ethane is added tothe resulting suspended liquid. Then, the reaction mixed solution isstirred for 10 minutes, whereby the reaction solution is separated to anorganic layer and a water layer. The water layer is extracted using 50ml of 1,2-diethoxy ethane and the organic layer thus obtained is mixedwith another organic layer which has been separated before.

The mixed organic layer is dried with magnesium sulfate anhydride, andthe solvent is distilled out under reduced pressure, whereby light-browncrystals of a tetrakis(pentafluorophenyl)borate.sodium.1,2-diethoxyethane complex are obtained as thetetrakis(fluoroaryl)borate.polyfunctional ether complex.

The yield and purity of thetetrakis(pentafluorophenyl)borate.sodium.1,2-diethoxy ethane complexanalyzed in the same manner as Example 17 are 94.2 mol % and 99%,respectively. Also, a mole ratio oftetrakis(pentafluorophenyl)borate.sodium and 1,2-diethoxy ethane in thetetrakis(pentafluorophenyl)borate.sodium.1,2-diethoxy ethane complex is1:3.

The tetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethanecomplex is identified with the following analysis data,

melting point: 167° C.-169° C. IR (KBr, cm⁻¹): 2986, 2940, 1645, 1516,1465, 1275, 1119, 1085, 1066, 980 ¹⁹F-NMR (DMSO-d₆, δ): −55.5, −84.6,−89.3 ¹H-NRM (DMSO-d₆, δ): 1.13 (6H, t, J = 7.2 Hz), 3.45 (4H, q, J =7.2 Hz), 3.49 (4H, s).

EXAMPLE 22

Here, 20 ml of a solution of di-n-butyl ether containing 0.004 mol oftetrakis(pentafluorophenyl)borate.potassium is charged to a reactionvessel of the same type as the one used in Example 17. Then, 0.020 molof 1,2-diethoxy ethane is added to the above solution, and the reactionsolution is stirred for 10 hours at room temperature, whereby thereaction solution is crystallized. The crystals are collected bysubjecting the content in the reaction vessel to the suction filtration,and then washed with 10 ml of di-n-butyl ether.

Then, the washed crystals are dried under reduced pressure, wherebywhite crystals of atetrakis(pentafluorophenyl)borate.potassium.1,2-diethoxy ethane complexare obtained as the tetrakis(fluoroaryl)borate.polyfunctional ethercomplex.

The yield and purity of thetetrakis(pentafluorophenyl)borate.potassium.1,2-diethoxy ethane complexanalyzed in the same manner as Example 17 are 70.7 mol % and 99.9%,respectively. Also, a mole ratio oftetrakis(pentafluorophenyl)borate.potassium and 1,2-diethoxy ethane inthe tetrakis(pentafluorophenyl)borate.potassium.1,2-diethoxy ethanecomplex is 1:3.

The tetrakis(pentafluorophenyl)borate.potassium.1,2-dimethoxy ethanecomplex is identified with the following analysis data,

melting point: 113° C.-114° C. IR (KBr, cm⁻¹): 2983, 2935, 1645, 1515,1464, 1276, 1085, 978 ¹⁹F-NMR (DMSO-d₆, δ): −56.6, −85.6, −90.1 ¹H-NRM(DMSO-d₆, δ): 1.11 (6H, t, J = 7.2 Hz), 3.44 (4H, q, J = 7.2 Hz), 3.45(4H, s).

EXAMPLE 23

Here, 20 ml of a solution of di-n-butyl ether containing 0.004 mol oftetrakis(pentafluorophenyl)borate.lithium is charged to a reactionvessel of the same type as the one used in Example 17. Then, 0.016 molof diethylene glycol dimethyl ether serving as the polyfunctional etheris added to the above solution, and the reaction solution is stirred for10 hours at room temperature, whereby the reaction solution iscrystallized. The crystals are collected by subjecting the content inthe reaction vessel to the suction filtration, and then washed with 10ml of di-n-butyl ether.

Then, the washed crystals are dried under reduced pressure, wherebywhite crystals of a tetrakis(pentafluorophenyl)borate.lithium.diethyleneglycol dimethyl ether complex are obtained as thetetrakis(fluoroaryl)borate.polyfunctional ether complex.

The yield and purity of thetetrakis(pentafluorophenyl)borate.lithium.diethylene glycol dimethylether complex analyzed in the same manner as Example 17 are 85.0 mol %and 99%, respectively. Also, a mole ratio oftetrakis(pentafluorophenyl)borate.lithium and diethylene glycol dimethylether in the tetrakis(pentafluorophenyl)borate.lithium.diethylene glycoldimethyl ether complex is 1:2.5.

The tetrakis(pentafluorophenyl)borate.lithium.diethylene glycol dimethylether complex is identified with the following analysis data,

melting point: 193° C.-195° C. IR (KBr, cm⁻¹): 2940, 1644, 1515, 1464,1279, 1114, 1084, 979 ¹⁹F-NMR (CDCl₃, δ): −56.7, −87.3, −91.1 ¹H-NRM(CDCl₃, δ): 3.36 (6H, s) 3.54-3.56 (4H, m) 3.63-3.65 (4H, m).

EXAMPLE 24

Here, 20 ml of a solution of di-n-butyl ether containing 0.005 mol oftetrakis(pentafluorophenyl)borate.sodium is charged to a reaction vesselof the same type as the one used in Example 17. Then, 0.016 mol ofdiethylene glycol dimethyl ether is added to the above solution, and thereaction solution is stirred for 10 hours at room temperature, wherebythe reaction solution is crystallized. The crystals are collected bysubjecting the content in the reaction vessel to the suction filtration,and then washed with 10 ml of di-n-butyl ether.

Then, the washed crystals are dried under reduced pressure, wherebywhite crystals of a tetrakis(pentafluorophenyl)borate.sodium.diethyleneglycol dimethyl ether complex are obtained as thetetrakis(fluoroaryl)borate.polyfunctional ether complex.

The yield and purity of thetetrakis(pentafluorophenyl)borate.sodium.diethylene glycol dimethylether complex analyzed in the same manner as Example 17 are 85.4 mol %and 99%, respectively. Also, a mole ratio oftetrakis(pentafluorophenyl)borate.sodium and diethylene glycol dimethylether in the tetrakis (pentafluorophenyl)borate.sodium.diethylene glycoldimethyl ether complex is 1:3.

The tetrakis(pentafluorophenyl)borate.sodium.diethylene glycol dimethylether complex is identified with the following analysis data,

melting point: 167° C.-169° C. IR (KBr, cm⁻¹): 2941, 1644, 1514, 1461,1276, 1113, 1085, 977 ¹⁹F-NMR (CDCl₃, δ): −56.4, −87.3, −91.3 ¹H-NRM(CDCl₃, δ): 3.38 (6H, s) 3.38-3.57 (4H, m) 3.59-3.61 (4H, m).

EXAMPLE 25

Here, 20 ml of a solution of di-n-butyl ether containing 0.005 mol oftetrakis(pentafluorophenyl)borate.potassium is charged to a reactionvessel of the same type as the one used in Example 17. Then, 0.016 molof diethylene glycol dimethyl ether is added to the above solution, andthe reaction solution is stirred for 10 hours at room temperature,whereby the reaction solution is crystallized. The crystals arecollected by subjecting the content in the reaction vessel to thesuction filtration, and then washed with 10 ml of di-n-butyl ether.

Then, the washed crystals are dried under reduced pressure, wherebywhite crystals of atetrakis(pentafluorophenyl)borate.potassium.diethylene glycol dimethylether complex are obtained as thetetrakis(fluoroaryl)borate.polyfunctional ether complex.

The yield and purity of thetetrakis(pentafluorophenyl)borate.potassium.diethylene glycol dimethylether complex analyzed in the same manner as Example 17 are 98.5 mol %and 99%, respectively. Also, a mole ratio oftetrakis(pentafluorophenyl)borate.potassium and diethylene glycoldimethyl ether in thetetrakis(pentafluorophenyl)borate.potassium.diethylene glycol dimethylether complex is 1:3.

The tetrakis(pentafluorophenyl)borate.potassium.diethylene glycoldimethyl ether complex is identified with the following analysis data,

melting point: 96° C.-97° C. IR (KBr, cm⁻¹): 2940, 2906, 1645, 1514,1465, 1276, 1110, 1087, 980 ¹⁹F-NMR (CDCl₃, δ): −56.9, −87.1, −91.1¹H-NRM (CDCl₃, δ): 3.33 (6H, s) 3.51-3.53 (4H, m) 3.55-3.58 (4H, m).

EXAMPLE 26

Here, a mixed solution is prepared by dissolving 0.259 mol oftetrakis(pentafluorophenyl)borate.magnesium bromide serving astetrakis(fluoroaryl)borate and 0.0194 mol of magnesium bromide fluorideinto a mixed solvent of diethyl ether and di-n-butyl ether (a volumeratio of diethyl ether and di-n-butyl ether: 1:1), and 100 ml of whichis charged to a reaction vessel of the same type as the one used inExample 17. Meanwhile, 0.0550 mol of 1,2-dimethoxy ethane is charged tothe dropping funnel.

Then, 1,2-dimethoxy ethane in the dropping funnel is dropped to thecontent in the reaction vessel over 15 minutes at room temperature withstirring of the content, and the content in the reaction vessel isheated to 140° C. with stirring, so that diethyl ether and excessive1,2-dimethoxy ethane are distilled out. After the reaction mixture iscooled to room temperature and crystallized, the crystals are collectedby subjecting the reaction mixture to the suction filtration, and thenwashed with 100 ml of di-n-butyl ether.

The washed crystals are dried under reduced pressure, wherebylight-yellow powders of a tetrakis(pentafluorophenyl)borate.magnesiumbromide.1,2-dimethoxy ethane complex are obtained as thetetrakis(fluoroaryl)borate.polyfunctional ether complex.

The yield and purity of the tetrakis (pentafluorophenyl)borate.magnesiumbromide-1,2-dimethoxy ethane complex analyzed in the same manner asExample 17 are 94.5 mol % and 99%, respectively. Thetetrakis(pentafluorophenyl)borate.magnesium bromide-1,2-dimethoxy ethanecomplex is analyzed through the X-ray fluorescence analysis, and nomagnesium is detected, meaning that magnesium bromide fluoride iscompletely removed. The data obtained by the analysis are:

melting point: 230° C. or above IR (KBr, cm⁻¹): 2953, 1631, 1516, 1465,1112, 1087, 980 ¹⁹F-NMR (CDCl₃, δ): −56.6, −87.6, −90.1 ¹H-NRM (CDCl₃,δ): 3.26 (6H, s) 3.44 (4H, s).

EXAMPLE 27

Here, 100 ml of a solution of di-n-butyl ether containing 0.040 mol of ahydrogen compound of tetrakis(pentafluorophenyl)borate.hydride ischarged to a reaction vessel of the same type as the one used in Example17. Meanwhile, 0.140 mol of 1,2-dimethoxy ethane is charged to thedripping funnel.

Then, 1,2-dimethoxy ethane in the dropping funnel is dropped to thecontent in the reaction vessel over 15 minutes at room temperature withstirring of the content, and the reaction solution is stirred forfurther one hour at the same temperature (room temperature). When thestirring ends, the content in the reaction vessel is heated underreduced pressure, so that di-n-butyl ether and excessive 1,2-dimethoxyethane are distilled out.

Subsequently, the content is cooled to room temperature, wherebylight-brown oil of a tetrakis(pentafluorophenyl)borate.1,2-dimethoxyethane complex is obtained.

The yield and purity of thetetrakis(pentafluorophenyl)borate.1,2-dimethoxy ethane complex analyzedin the same manner as Example 17 are 90.0 mol % and 98%, respectively.The data obtained by the analysis are,

¹⁹F-NMR (CDCl₃, δ): −56.8, −87.4, −91.3 ¹H-NRM (CDCl₃, δ): 3.39 (6H, s)3.60 (4H, s) 9.83 (1H, br).

EXAMPLE 28

Here, 108 g of a solution of di-n-butyl ether containing 32.43 wt %(0.050 mol) of tetrakis(pentafluorophenyl)borate.sodium is charged to areaction vessel of the same type as the one used in Example 17.Meanwhile, 0.100 mol of 1,2-dimethoxy ethane is charged to the droppingfunnel.

Then, 1,2-dimethoxy ethane in the dropping funnel is dropped to thecontent in the reaction vessel over 10 minutes at 20° C. while thecontent in the reaction vessel is stirred at room temperature, and thereaction solution is stirred for further 10 hours at the sametemperature (room temperature), whereby the reaction solution iscrystallized. The crystals are collected by subjecting the content inthe reaction vessel to the suction filtration, and then washed with 18 gof di-n-butyl ether.

The washed crystals are dried under reduced pressure, wherebylight-yellow crystals of atetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexare obtained.

The yield and purity of thetetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexanalyzed in the same manner as Example 17 are 70.0 mol % and 99%,respectively.

EXAMPLE 29

Here, 108 g of a solution of di-n-butyl ether containing 32.43 wt %(0.050 mol) of tetrakis(pentafluorophenyl)borate.sodium is charged to areaction vessel of the same type as the one used in Example 17.Meanwhile, 0.150 mol of 1,2-dimethoxy ethane is charged to the droppingfunnel. Then, 1,2-dimethoxy ethane in the dropping funnel is dropped tothe content in the reaction vessel over 10 minutes at 20° C. while thecontent is stirred at room temperature, and the reaction solution isstirred for further 10 hours at the same temperature (room temperature),whereby the reaction solution is crystallized.

The crystals are collected by subjecting the content in the reactionvessel to the suction filtration, and then washed with 18 g ofdi-n-butyl ether. The washed crystals are dried under reduced pressure,whereby white crystals of atetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexare obtained.

The yield and purity of thetetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexanalyzed in the same manner as Example 17 are 85.8 mol % and 99%,respectively.

EXAMPLE 30

Here, 90 g of a solution of di-n-butyl ether containing 22.0 wt % (0.028mol) of tetrakis(pentafluorophenyl)borate.sodium is charged to areaction vessel of the same type as the one used in Example 17.Meanwhile, 0.098 mol of 1,2-dimethoxy ethane is charged to the droppingfunnel. Then, 1,2-dimethoxy ethane in the dropping funnel is dropped tothe content in the reaction vessel over 10 minutes at 20° C. while thecontent is stirred at room temperature, and the reaction solution isstirred for further 10 hours at the same temperature (room temperature),whereby the reaction solution is crystallized.

The crystals are collected by subjecting the content in the reactionvessel to the suction filtration, and then washed with 10 g ofdi-n-butyl ether. The washed crystals are dried under reduced pressure,whereby white crystals of atetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexare obtained.

The yield and purity of thetetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexanalyzed in the same manner as Example 17 are 95.3 mol % and 99%,respectively.

EXAMPLE 31

Here, 0.0152 mol oftetrakis(pentafluorophenyl)borate.potassium.1,2-dimethoxy ethane complexserving as the tetrakis(fluoroaryl)borate.ether complex and 100 ml of amixed solvent of acetone and ion-exchange water (mixing volume ratio:1:1) are charged to a reaction vessel equipped with a thermometer, adropping funnel, a distillation device, and a stirrer. Meanwhile, 20 mlof an aqueous solution of N,N-dimethylaniline.hydrochloride (an amountof N,N-dimethylaniline.hydrochloride is 0.0167 mol) serving as thecation seed generating compound is charged to the dropping funnel.

Then, the content in the reaction vessel is heated at 90° C. for 30minutes with stirring, so that 1,2-dimethoxy ethane and acetone aredistilled out from the reaction series through the distillation device,whereby an aqueous solution oftetrakis(pentafluorophenyl)borate.potassium is obtained astetrakis(fluoroaryl)borate.

Subsequently, the aqueous solution of N,N-dimethylaniline.hydrochloridein the dropping funnel is dropped to the content in the reaction vesselover 10 minutes at the same temperature (90° C.), and the resultingmixed solution is stirred for further 30 minutes at the same temperature(90° C.). Then, after the reaction solution is cooled to roomtemperature and crystallized, the content in the reaction vessel issubjected to the suction filtration, and the resulting cake is washedwith ion-exchange water.

Then, the washed cake is dried under reduced pressure, whereby whitepowders of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate isobtained as the tetrakis(fluoroaryl)borate derivative.

The yield of the N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate thus obtained is found bymeasuring ¹⁹F-NMR (Nuclear, Magnetic Resonance) spectrum. In otherwords, ¹⁹F-NMR is measured under predetermined conditions usingp-fluorotoluene as the internal standard reagent. Then, a ratio of apeak integral of a fluorine atom of p-fluorotoluene, and a peak integralof fluorine atoms at the ortho-position of a pentafluorophenyl group inN,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate is computedfrom the resulting ¹⁹F-NMR chart first, and thence a weight ofN,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate is computedusing the above peak integral ratio.

The yield of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)boratebased on the tetrakis(pentafluorophenyl)borate.potassium.1,2-dimethoxyethane complex thus found is 92.5 mol % and the purity of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate is 99%.

EXAMPLE 32

Here, 0.0446 mol of thetetrakis(pentafluorophenyl)borate.potassium.1,2-dimethoxy ethane complexand 200 g of ion-exchange water are charged to a reaction vessel of thesame type as the one used in Example 31, and the content is stirred,whereby a suspended liquid is obtained.

Subsequently, the suspended,liquid is heated with stirring, so that1,2-dimethoxy ethane is distilled out through the distillation device,after which the content is cooled to 50° C. As a consequence, an aqueoussolution of tetrakis(pentafluorophenyl)borate.potassium is obtained astetrakis(fluoroaryl)borate.

Then, 80 ml of an aqueous solution of N,N-dimethylaniline sulfate (anamount of N,N-dimethyl aniline sulfate is 0.060 mol) serving as thecation seed generating compound is charged to the dropping funnel. Then,the aqueous solution of N,N-dimethylaniline sulfate is dropped to theaqueous solution of tetrakis(pentafluorophenyl)borate.potassium at 50°C. with stirring. Then, after the reaction solution is cooled to roomtemperature and crystallized, the content in the reaction vessel issubjected to the suction filtration, after which the resulting cake iswashed with ion-exchange water.

Further, the washed cake is dried under reduced pressure, whereby whitepowders of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate areobtained. The yield and purity of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate analyzed in the same manneras Example 31 are 90.9 mol % and 99%, respectively.

EXAMPLE 33

Here, 2.29 mmol of thetetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexserving as the tetrakis(fluoroaryl)borate.ether complex and 40 ml ofdi-n-butyl ether are charged to a reaction vessel of the same type asthe one used in Example 31. The content is stirred and a mixed solutionis obtained. Meanwhile, 10 ml of an aqueous solution ofN,N-dimethylaniline.hydrochloride (an amount ofN,N-dimethylaniline.hydrochloride is 3.51 mmol) is charged to thedropping funnel.

Then, the aqueous solution of N,N-dimethylaniline.hydrochloride in thedropping funnel is dropped to the mixed solution at room temperaturewith stirring of the mixed solution. When the dropping ends, the mixedliquid in the reaction vessel is heated, so that 1,2-dimethoxy ethane isdistilled out through the distillation device.

Subsequently, the reaction solution is cooled to room temperature andseparated to a di-n-butyl ether layer and a water layer. The di-n-butylether layer is distilled out from the di-n-butyl ether layer underreduced pressure, whereby the di-n-butyl ether layer is crystallized.The crystals are collected by subjecting the content in the reactionvessel to the suction filtration, and then washed with a slight amountof di-n-butyl ether.

The washed crystals are dried overnight at 80° C. under reducedpressure, whereby white powders of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate are obtained. The yield andpurity of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borateanalyzed in the same manner as Example 31 are 58.8 mol % and 99%,respectively.

EXAMPLE 34

Here, a solution is prepared by dissolving 0.123 mol of thetetrakis(pentafluorophenyl)borate.lithium.1,2-diethoxy ethane complexserving as the tetrakis (fluoroaryl)borate.ether complex into a mixedsolvent of acetone and ion-exchange water (mixing volume ratio: 1:1),and 300 ml of which is charged to a reaction vessel equipped with athermometer, a dropping funnel, a reflux condensing pipe, and a stirrer.Meanwhile, 100 ml of an aqueous solution ofN,N-dimethylaniline-hydrochloride (an amount ofN,N-dimethylaniline-hydrochloride is 0.135 mol) is charged to thedropping funnel.

Then, the aqueous solution of N,N-dimethylaniline.hydrochloride in thedropping funnel is dropped to the content in the reaction vessel over 30minutes at room temperature with stirring of the content, and thereaction solution is stirred for further 30 minutes at the sametemperature (room temperature), whereby the reaction solution iscrystallized. The content in the reaction vessel is subjected to thesuction filtration, and the resulting cake is washed with ion-exchangewater.

The washed cake is dried under reduced pressure, whereby white powdersof an N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-diethoxy ethane complexare obtained as the tetrakis(fluoroaryl)borate derivative-ether complex.

The yield and purity of the N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-diethoxy ethane complexanalyzed in the same manner as Example 31 are 49.8 mol % and 99%,respectively.

Further, ¹H-NMR is measured under predetermined conditions usingp-fluorotoluene as the internal standard reagent. Then, a ratio of apeak integral of a methyl group of p-fluorotoluene, a peak integral ofmethyl groups of N,N-dimethylaniline, and a peak integral of a methylgroup of 1,2-diethoxy ethane is computed from the resulting ¹H-NMR chartfirst, and thence weights of N,N-dimethylaniline and 1,2-diethoxy ethaneare computed using the above peak integral ratio. A mole ratio ofN,N-dimethyl anilinium tetrakis(pentafluorophenyl)borate and1,2-diethoxy ethane in the N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-diethoxy ethane complexfound based on the weights of N,N-dimethylaniline and 1,2-diethoxyethane is 1:1.

Meanwhile, the filtrate obtained by the above filtration is concentratedunder reduced pressure, whereby white crystals of the N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-diethoxy ethane complexare collected. The yield of the collected complex is 45.0 mol % (therebymaking a total yield of 94.8 mol %).

The N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-diethoxy ethane complexis identified through the analysis of the measured melting point, IR(Infrared absorption spectrum), ¹⁹F-NMR, and ¹H-NRM. The data obtainedthrough the analysis are,

melting point: 162° C.-163° C. IR (KBr, cm⁻¹): 2984, 2941, 1644, 1515,1465, 1277, 1112, 1069, 980 ¹⁹F-NMR (CDCl₃, δ): −56.8, −87.1, −91.0¹H-NRM (CDCl₃, δ): 1.22 (6H, t, J = 7.2 Hz), 3.22 (6H, s), 3.40-3.68(8H, m), 7.31-7.33 (2H, m), 7.56-7.59 (3H, m).

EXAMPLE 35

Here, 0.0188 mol of thetetrakis(pentaflurophenyl)borate.potassium.1,2-dimethoxy ethane complexis charged to a reaction vessel of the same type as the one used inExample 34, and suspended in 50 ml of ion-exchange water. Meanwhile, 20ml of an Aqueous solution of N,N-dimethylaniline.hydrochloride (anamount of N,N-dimethylaniline.hydrochloride is 0.0207 mol) is charged tothe dropping funnel.

Then, the aqueous solution of N,N-dimethylaniline.hydrochloride in thedropping funnel is dropped to the suspended liquid over 30 minutes atroom temperature with stirring of the suspended liquid, and the reactionsolution is stirred for further 30 minutes at the same temperature (roomtemperature), whereby the reaction solution is crystallized. The contentin the reaction vessel is subjected to the suction filtration and theresulting cake is washed with ion-exchange water.

The washed cake is dried under reduced pressure, whereby white powdersof an N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-dimethoxy ethane complexare obtained as the tetrakis(fluoroaryl)borate derivative.ether complex.

The yield and purity of the N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-dimethoxy ethane complexanalyzed in the same manner as Example 31 are 93.1 mol % and 99%,respectively.

Further, a mole ratio of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate and 1,2-dimethoxy ethane inthe N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-dimethoxy ethane complexfound in the same manner as Example 34 is 1:1.

The N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-dimethoxy ethane complexis identified with the following analysis data,

melting point: 129° C.-131° C. IR (KBr, cm⁻¹): 2952, 2908, 1646, 1517,1456, 1277, 1083, 978 ¹⁹F-NMR (CDCl₃, δ): −56.6, −85.5, −90.1 ¹H-NRM(CDCl₃, δ): 3.11 (6H, s) 3.25 (6H, s), 3.42 (4H, s), 7.20-7.50 (5H, m).

EXAMPLE 36

Here, 6.44 mmol of thetetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethane complexis charged to a reaction vessel of the same type as the one used inExample 34, to which 20 ml of acetone and 20 ml of ion-exchange waterare added to dissolve the complex. Meanwhile, 20 ml of an aqueoussolution of N,N-dimethylaniline.hydrochloride (an amount ofN,N-dimethylaniline.hydrochloride is 7.08 mmol) is charged to thedropping funnel.

Then, the aqueous solution of N,N-dimethylaniline.hydrochloride isdropped to the content in the reaction vessel over 10 minutes at roomtemperature with stirring of the content, and the reaction solution isstirred for further one hour at the same temperature (room temperature).Subsequently, the content in the reaction vessel is heated to 40° C.under reduced pressure, so that acetone is distilled out, after whichthe content is extracted using isopropyl ether. The extraction liquid isdried with magnesium sulfate anhydride. Then, magnesium sulfateanhydride is filtered out and isopropyl ether is distilled out underreduced pressure, whereby light-yellow oil of an N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-dimethoxy ethane complexis obtained.

The yield and purity of the N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-dimethoxy ethane complexanalyzed in the same manner as Example 31 are 82.8 mol % and 99%,respectively.

EXAMPLE 37

Here, 1.03 mmol of thetetrakis(pentafluorophenyl)borate.sodium.diethylene glycol dimethylether complex is charged to a reaction vessel of the same type as theone used in Example 34, to which 10 ml of ion-exchange water is added tosuspend the complex. Meanwhile, 10 ml of an aqueous solution ofN,N-dimethylaniline.hydrochloride (an amount ofN,N-dimethylaniline.hydrochloride is 1.23 mmol) is charged to thedropping funnel.

Then, the aqueous solution of N,N-dimethylaniline.hydrochloride isdropped to the content in the reaction vessel over 10 minutes at roomtemperature with stirring of the content, and the reaction solution isstirred for further one hour at room temperature, whereby the reactionsolution is crystallized. The content in the reaction vessel issubjected to the suction filtration, and the resulting cake is washedwith ion-exchange water.

Then, the washed cake is dried under reduced pressure, whereby whitepowders of an N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.diethylene glycol dimethylether complex are obtained as the tetrakis(fluoroaryl)boratederivative.ether complex.

The yield and purity of the N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.diethylene glycol dimethylether complex analyzed in the same manner as Example 31 are 89.3 mol %and 99%, respectively.

Further, a mole ratio of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate and diethylene glycoldimethyl ether in the N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.diethylene glycol dimethylether complex found in the same manner as Example 34 is 1:1.

The N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate.diethyleneglycol dimethyl ether complex is identified with the following analysisdata,

melting point: 179° C.-180° C. IR (KBr, cm⁻¹): 2940, 2904, 1644, 1515,1468, 1462, 1278, 1114, 1084, 978 ¹⁹F-NMR (CDCl₃, δ): −56.8, −87.1,−91.0 ¹H-NRM (CDCl₃, δ): 3.25 (6H, s), 3.38 (6H, s), 3.41-3.58 (4H, m),3.59-3.66 (4H, m), 7.34-7.36 (2H, m), 7.57-7.58 (3H, m).

EXAMPLE 38

Here, a solution of acetone is prepared by dissolving 6.44 mmol of thetetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethane complexis dissolved into acetone, and 30 ml of which is charged to a reactionvessel of the same type as the one used in Example 31.

The content in the reaction vessel is heated for 30 minutes withstirring, so that 1,2-dimethoxy ethane and acetone are distilled out;from the reaction series through the distillation device. Further, atemperature inside the reaction vessel is heated to 100° C. andsubsequently cooled to room temperature.

Consequently, light-yellow oil oftetrakis(pentafluorophenyl)borate.lithium is obtained astetrakis(fluoroaryl)borate. The yield oftetrakis(pentafluorophenyl)borate.lithium analyzed in the same manner asExample 31 is 95.3 mol %.

EXAMPLE 39

Here, a solution is prepared by dissolving 5.34 mmol of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate.1,2-dimethoxy ethane complexobtained in Example 35 into a mixed solvent of acetone and ion-exchangewater (mixing volume ratio: 1:1), and 40 ml of which is charged to areaction vessel of the same type as the one used in Example 31.

A temperature inside the reaction vessel is raised to 80° C. while thecontent in the reaction vessel is stirred. Then, after the temperature(80° C.) is maintained for 30 minutes, a pressure inside the reactionvessel is reduced at the same temperature (80° C.), so that1,2-dimethoxy ethane, acetone, and ion exchange water are distilled outfrom the reaction series.

Consequently, white powders of N,N-dimethylanilinium.tetrakis(pentaflurorphenyl)borate are obtained. The yield andpurity of N,N-dimethyl anilinium.tetrakis(pentaflurorphenyl)borateanalyzed in the same manner as Example 31 are 93.6 mol % and 99%,respectively.

EXAMPLE 40

Here, a solution is prepared by dissolving 1.24 mmol of thetetrakis(pentafluorophenyl)borate.lithium.1,2-dimethoxy ethane complexinto a mixed solvent of acetone and ion-exchange water (mixing volumeratio: 1:1), and 20 ml of which is charged to a reaction vessel of thesame type as the one used in Example 31. Meanwhile, 10 ml of an aqueoussolution of N,N-dimethylaniline.hydrochloride (an amount ofN,N-dimethylaniline.hydrochloride is 1.34 mmol) is charged to thedropping funnel.

Then, the aqueous solution of N,N-dimethylaniline.hydrochloride isdropped to the content in the reaction vessel over 10 minutes at roomtemperature with stirring of the content, and the reaction solution isstirred for further one hour at the same temperature (room temperature).Then, a temperature inside the reaction vessel is raised to 100° C. andthe temperature (100° C.) is maintained for 30 minutes, so that acetoneand 1,2-dimethoxy ethane are distilled out. After the reaction productis extracted using 20 ml of isopropyl ether, the extraction liquid isdried with magnesium sulfate anhydride. Then, after magnesium sulfateanhydride is filtered out, isopropyl ether is distilled out underreduced pressure.

Consequently, light-brown crystals of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate are obtained. The yield andpurity of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borateanalyzed in the same manner as Example 31 are 95.6 mol % and 99%,respectively.

EXAMPLE 41

Here, a solution is prepared by dissolving 0.0152 mol oftetrakis(pentafluorophenyl)borate.potassium.1,2-dimethoxy ethane complexinto a mixed solvent of acetone and ion-exchange water (mixing volumeratio: 1:1), and 100 ml of which is charged to a reaction vessel of thesame type as the one used in Example 31. Meanwhile, 20 ml of an aqueoussolution of N,N-dimethylaniline.hydrochloride (an amount ofN,N-dimethylaniline.hydrochloride is 0.0167 mol) is charged to thedropping funnel.

Then, a temperature inside the reaction vessel is raised to 90° C. whilethe content in the reaction vessel is stirred, and the content isstirred for further 90 minutes at the same temperature (90° C.), so thatacetone and 1,2-dimethoxy ethane are distilled out.

Then, the aqueous solution of N,N-dimethylaniline.hydrochloride isdropped to the content over 30 minutes at the same temperature (90° C.),after which a temperature inside the reaction vessel is cooled to roomtemperature to crystallize the reaction solution. The crystals arecollected by subjecting the content in the reaction vessel to thesuction filtration, and then washed with 100 ml of ion-exchange water.

The washed crystals are dried at 90° C. under reduced pressure, wherebylight-yellow crystals of N,N-dimethylanilinium.tetrakis(pentafluorophenyl)borate are obtained. The yield andpurity of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borateanalyzed in the same manner as Example 31 are 94.0 mol % and 99%,respectively.

EXAMPLE 42

Here, 0.0103 mol of thetetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexand 50 ml of ion-exchange water are charged to a reaction vessel of thesame type as the one used in, Example 31. Then, the content is stirred,whereby a suspended liquid is obtained.

Subsequently, the suspended liquid is heated with stirring, so that1,2-dimethoxy ethane is distilled out through the distillation device,whereby an aqueous solution of tetrakis(pentafluorophenyl)borate.sodiumis obtained as tetrakis(fluoroaryl)borate.

After the aqueous solution is cooled to 55° C., the distillation deviceof the reaction vessel is switched to the reflux condenser, while 0.0103mol of tetraphenyl phosphonium bromide serving as the cation seedgenerating compound and 60 ml of acetone are added to the aqueoussolution with stirring, whereby a suspended liquid is obtained.

The suspended liquid is heated with stirring, and refluxed over 1.5hour. Further, the reflux condenser of the reaction vessel is switchedto the distillation device at the reflux temperature. Consequently, 35.4g of the solvent is distilled out. After the temperature inside thereaction vessel is cooled to room temperature and the reaction solutionis crystallized, the content in the reaction vessel is subjected to thesuction filtration, and the resulting cake is washed with ion-exchangewater.

Then, the washed cake is dried at 80° C. under reduced pressure, wherebywhite crystals of tetraphenylphosphonium.tetrakis(pentafluorophenyl)borate are obtained. The yieldand purity of tetraphenyl phosphonium.tetrakis(pentafluorophenyl)borateanalyzed in the same manner as Example 31 are 96.3 mol % and 99%,respectively.

EXAMPLE 43

Here, 0.015 mol of thetetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexand 50 ml of ion-exchange water are charged to a reaction vessel of thesame type as the one used in Example 31. Then, the content is stirred,whereby a suspended liquid is obtained.

Subsequently, the suspended liquid is heated with stirring, so that1,2-dimethoxy ethane is distilled out through the distillation device,whereby an aqueous solution of tetrakis(pentaflurorphenyl)borate.sodiumis obtained.

After the aqueous solution is cooled to room temperature, anotheraqueous solution containing 0.016 mol of quinoline.hydrochloride servingas the cation seed generating compound is added to the cooled aqueoussolution, and the resulting mixed aqueous solution is stirred for onehour. Then, the content in the reaction vessel is subjected to thesuction filtration, and the resulting cake is washed with ion-exchangewater.

Then, the washed cake is dried at 80° C. under reduced pressure, wherebywhite crystals of quinolinium.tetrakis(pentafluorophenyl)borate areobtained. The yield and purity of quinolinium.tetrakis(pentafluorophenyl)borate analyzed in the same manner as Example 31 are82.3 mol % and 99%, respectively.

EXAMPLE 44

The reaction and manipulation are carried out in the same manner asExample 43 except that the used aqueous solution contains 0.016 mol ofN-methyl pyridine iodide as the cation seed generating compound insteadof quinoline.hydrochloride. Consequently, white crystals of N-methylpyridinium.tetrakis(pentaflurorphenyl)borate are obtained. The yield andpurity of N-methyl pyridinium.tetrakis(pentaflurorphenyl)borate analyzedin the same manner as Example 31 are 54.7 mol % and 99%, respectively.

EXAMPLE 45

The reaction and manipulation are carried out in the same manner asExample 43 except that the aqueous used instead of the aqueous solutionof quinoline.hydrochloride contains 0.016 mol of trimethyl sulfoniumiodide as the cation seed generating compound. Consequently, whitecrystals of trimethyl sulfonium.tetrakis(pentaflurorphenyl)borate areobtained. The yield and purity of trim ethyl sulfoniumtetrakis(pentafluorophenyl)borate analyzed in the same manner as Example31 are 89.5 mol % and 99%, respectively.

EXAMPLE 46

Here, 0.017 mol oftetrakis(pentafluorophenyl)borate.sodium.1,2-dimethoxy ethane complexand 50 ml of ion-exchange water are charged to a reaction vessel of thesame type as the one used in Example 31. Then, the content is stirred,whereby a suspended liquid is obtained.

Subsequently, the suspended liquid is heated with stirring, so that1,2-dimethoxy ethane is distilled out through the distillation device,whereby an aqueous solution of tetrakis(pentafluorophenyl)borate.sodiumis obtained.

After the aqueous solution is cooled to room temperature, 0.016 mol ofdiphenyl iodonium chloride serving as the cation seed generatingcompound is added to the aqueous solution, and the reaction solution isstirred for three hours. Then, the content in the reaction vessel issubjected to the suction filtration, and the resulting cake is washedwith ion-exchange water.

The washed cake is dried at 80° C. under reduced pressure, whereby whitecrystals of diphenyl iodonium.tetrakis(pentafluorophenyl)borate areobtained. The yield and purity of diphenyliodonium.tetrakis(pentafluorophenyl)borate analyzed in the same manneras Example 31 are 92.3 mol % and 99%, respectively.

EXAMPLE 47

An aqueous solution of tetrakis(pentafluorophenyl)borate.sodium isobtained by carrying out the manipulation in the same manner as Example46. The aqueous solution is solidified at 100° C. under reducedpressure, whereby 11.9 g of solidtetrakis(pentafluorophenyl)borate.sodium is obtained.

Then, the solid is suspended in 200 ml of n-hexane, and 0.019 mol oftrityl chloride serving as the cation seed generating compound is addedto the suspended liquid, after which the suspended liquid is stirred forsix hours at the reflux temperature. After the suspended liquid iscooled to room temperature, the content in the reaction vessel issubjected to the suction filtration, and the resulting cake is dissolvedinto dichloromethane.

Then, an insoluble component (deposit) contained in the cake is removedthrough the suction filtration, and the resulting filtrate isconcentrated under reduced pressure. Then, n-hexane is added to theconcentrate until it is crystallized. After the crystals are allowed tostand for 16 hours, the content in the reaction vessel is subjected tothe suction filtration, and the resulting cake is washed with n-hexane.

Then, the washed cake is dried at 80° C. under reduced pressure, wherebyyellow crystals of trityl.tetrakis(pentafluorophenyl)borate areobtained. The yield and purity oftrityl.tetrakis(pentafluorophenyl)borate analyzed in the same manner asExample 31 are 30.6 mol % and 99%, respectively.

Example embodiment and examples disclosed in THE BEST MODE FORIMPLEMENTING THE INVENTION clause are provided to make the art, of thepresent invention apparent. Thus, the present invention shall not beconstrued limitedly to these examples and can be modified in many wayswithin the spirit of the present invention and the scope of the claimsset forth below.

POSSIBLE INDUSTRIAL APPLICATION

The tetrakis(fluoroaryl)borate.ether complex andtetrakis(fluoroaryl)borate derivative obtained by the producingprocesses of the present invention are useful as, for example: aco-catalyst of the metallocene catalyst (polymeric catalyst) used in thecationic complex polymerization reaction; a photopolymeric catalyst forsilicone; a cationic polymerization initiator used for thepolymerization of a functional polymer or monomer through photochemicalactivation or irradiation of electronic beams; an intermediate forproducing tetrakis(pentafluorophenyl)borate derivatives of variouskinds; etc.

What is claimed is:
 1. A tetrakis(fluoroaryl)borate.ether complex ofFormula (4):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, each of R₁₁ and R₁₂ represents a hydrocarbon group whichmay include a substituent group containing a hetero atom, Y represents abivalent hydrocarbon group, M represents a hydrogen atom, an alkalimetal, an alkaline earth metal, or alkaline earth metal halide, nrepresents 2 or 3, and m represents 1 when M represents a hydrogen atom,alkali metal, or alkaline earth metal halide, and 2 when M represents analkaline earth metal.
 2. A process for producing atetrakis(fluoroaryl)borate.ether complex of Formula (4):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, each of R₁₁ and R₁₂ represents a hydrocarbon group whichmay include a substituent group containing a hetero atom, Y represents abivalent hydrocarbon group, M represents a hydrogen atom, an alkalimetal, an alkaline earth metal, or an alkaline earth metal halide, nrepresents 2 or 3, and m represents 1 when M represents a hydrogen atom,an alkali metal, or an alkaline earth metal halide, and 2 when Mrepresents an alkaline earth metal, comprising: reactingtetrakis(fluoroaryl)borate of Formula (5):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, M represents a hydrogen atom, an alkali metal, analkaline earth metal, or an alkaline earth metal halide, n represents 2or 3, and m represents 1 when M represents a hydrogen atom, an alkalimetal, or an alkaline earth metal halide, and 2 when M represents analkaline earth metal, with an ether compound of Formula (6):R₁₁—O—Y—O—R₁₂  (6) where each of R₁₁ and R₁₂ represents a hydrocarbongroup which may include a substituent group containing a hetero atom,and Y represents a bivalent hydrocarbon group.
 3. The process forproducing a tetrakis(fluoroaryl)borate.ether complex of claim 2, whereinsaid tetrakis(fluoroaryl)borate is a hydrogen compound oftetrakis(pentafluorophenyl)borate,tetrakis(pentafluorophenyl)borate.magnesium bromide,tetrakis(pentafluorophenyl)borate.lithium,tetrakis(pentafluorophenyl)borate.sodium, ortetrakis(pentafluorophenyl)borate.potassium.
 4. The process forproducing a tetrakis(fluoroaryl)borate.ether complex of claim 2, whereinsaid ether compound is selected from the group consisting of ethyleneglycol dialkyl ether, ethylene glycol dicyclo alkyl ether, diethyleneglycol dialkyl ether, triethylene glycol dialkyl ether, and ethyleneglycol diaryl ether and mixtures thereof.
 5. A process for producing atetrakis(fluoroaryl)borate derivative of Formula (2):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, Z⁺ represents a monovalent cationic compound, and nrepresents 2 or 3, comprising using, as a starting material, atetrakis(fluoroaryl)borate.ether complex of Formula (4):

 where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, each of R₁₁ and R₁₂ represents a hydrocarbon group whichmay include a substituent group containing a hetero atom, Y represents abivalent hydrocarbon group, M represents a hydrogen atom, an alkalimetal, an alkaline earth metal, or an alkaline earth metal halide, nrepresents 2 or 3, and m represents 1 when M represents a hydrogen atom,an alkali metal, or an alkaline earth metal halide, and 2 when Mrepresents an alkaline earth metal, and a compound generating monovalentcationic compounds.
 6. The process for producing atetrakis(fluoroaryl)borate derivative of claim 5, wherein saidmonovalent cationic compounds are selected from the group consisting ofammonium cations, anilinium cations, pyridinium cations, quinoliniumcations, phosphonium cations, sulfonium cations, iodonium cations,carbenium cations and mixtures thereof.
 7. The process for producing atetrakis(fluoroaryl)borate derivative of claim 5, wherein said compoundgenerating the monovalent cationic compounds is selected from the groupconsisting of a quaternary ammonium compound, a nitrogen-containingaromatic heterocyclic compound, a quaternary phosphonium compound, asulfonium compound, an iodonium compound, a carbenium compound andmixtures thereof.
 8. The process for producing atetrakis(fluoroaryl)borate derivative of claim 5, wherein said compoundgenerating the monovalent cationic compounds is selected from the groupconsisting of tri-n-butylamine.hydrochloride,N,N-dimethylaniline.hydrochloride, N,N-dimethylaniline.sulfate,quinoline.hydrochloride, N-methyl pyridine.iodide, tetraphenylphosphonium bromide, trimethyl sulfonium iodide, diphenyl iodoniumchloride, trityl chloride, and mixtures thereof.
 9. The process forproducing a tetrakis(fluoroaryl)borate derivative of claim 5, whereinsaid process includes the step of removing an ether compound of Formula(6): R₁₁—O—Y—O—R₁₂  (6) where each of R₁₁ and R₁₂ represents ahydrocarbon group which may include a substituent group containing ahetero atom, and Y represents a bivalent hydrocarbon group, from saidreaction.
 10. The process for producing a tetrakis(fluoroaryl)boratederivative of claim 9, wherein said ether compound is selected from thegroup consisting of ethylene glycol dialkyl ether, ethylene glycoldicyclo alkyl ether, diethylene glycol dialkyl ether, triethylene glycoldialkyl ether, ethylene glycol diaryl ether and mixtures thereof. 11.The process for producing a tetrakis(fluoroaryl)borate derivative ofclaim 9, wherein, after obtaining tetrakis(fluoroaryl)borate of Formula(5):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, M represents a hydrogen atom, an alkali metal, analkaline earth metal, or an alkaline earth metal halide, n represents 2or 3, and m represents 1 when M represents a hydrogen atom, an alkalimetal, or an alkaline earth metal halide, and 2 when M represents analkaline earth metal, by removing said ether compound from saidtetrakis(fluoroaryl)borate.ether complex, saidtetrakis(fluoroaryl)borate is reacted with said compound generating themonovalent cationic compounds.
 12. The process for producing atetrakis(fluoroaryl)borate derivative of claim 9, wherein, afterobtaining a tetrakis(fluoroaryl)borate derivative.ether complex ofFormula (7):

where each of R₁-R₁₀ represents a hydrogen atom, a fluorine atom, ahydrocarbon group, or an alkoxy group, provided that at least one ofR₁-R₅ represents a fluorine atom and at least one of R₆-R₁₀ represents afluorine atom, each of R₁₁ and R₁₂ represents a hydrocarbon group whichmay include a substituent group containing a hetero atom, Y represents abivalent hydrocarbon group, Z⁺ represents a monovalent cationiccompound, and n represents 2 or 3, by reacting saidtetrakis(fluoroaryl)borate.ether complex with said compound generatingthe monovalent cationic compound, said ether compound is removed fromsaid tetrakis(fluoroaryl)borate derivative.ether complex.